Steve M. Heald

Ferromagnetism in oxide semiconductors

Over the past five years, considerable work has been carried out in the exploration of candidate diluted oxide magnetic semiconductors with high Curie temperatures. Fueled by early experimental results and theoretical predictions, claims of ferromagnetism at and above room temperature in doped oxides have abounded. In general, neither the true nature of these materials nor the physical causes of the magnetism have been adequately determined. It is now apparent that these dilute magnetic systems are deceptively complex. We consider two well-characterizedn-type magnetically doped oxide semiconductors and explore the relationship between donor electrons and ferromagnetism.

Coprecipitation of Uranium(VI) with Calcite: XAFS, micro-XAS, and luminescence characterization

X-ray absorption and luminescence spectroscopies have been used to characterize the local structure and coordination of uranium(VI) species coprecipitated with calcite (CaCO3) from room-temperature aqueous solutions. Different solution chemistries and pHs are found to result in differences in the equatorial coordination of the uranyl species (UO2 ) incorporated in the calcite, with multiple coordination environ- ments of uranyl evident in one sample. Differences in the equatorial coordination between the aqueous uranyl species and those found in the calcite indicate that coordination changes occur during incorporation of at least some species. This contrasts with previous findings showing no change in equatorial coordination during uranyl incorporation into aragonite, and may explain the greater incorporation in this latter phase. The absence of calcium backscatterers and well defined structure beyond the equatorial shell is consistent with disorder associated with disruption of the local calcite structure. This may indicate an inability of the uranyl unit to assume a stable structural environment in the host calcite, which could decrease the stability of uranyl- containing calcite. Calcite single crystals grown in uranyl-containing solutions exhibit polygonized spiral growth hillocks on (101 ¯4) surfaces composed of four vicinal surfaces, consistent with face symmetry. Micro-X-ray fluorescence reveals that uranium is differentially incorporated between nonequivalent vicinal surfaces, reflecting step- selective incorporation of uranyl species during growth. Micro-X-ray absorption near-edge structure spectra from the nonequivalent vicinal faces fail to reveal any differences in speciation between the vicinals or that might account for the presence of the multiple coordination environments identified by luminescence and X-ray absorption spectroscopies. Copyright

(De)Lithiation Mechanism of Li/SeSx (x = 0–7) Batteries Determined by in Situ Synchrotron X-ray Diffraction and X-ray Absorption Spectroscopy

Electrical energy storage for transportation has gone beyond the limit of converntional lithium ion batteries currently. New material or new battery system development is an alternative approach to achieve the goal of new high-energy storage system with energy densities 5 times or more greater. A series of SeSx-carbon (x = 0-7) composite materials has been prepared and evaluated as the positive electrodes in secondary lithium cells with ether-based electrolyte. In situ synchrotron high-energy X-ray diffraction was utilized to investigate the crystalline phase transition during cell cycling. Complementary, in situ Se K-edge X-ray absorption near edge structure analysis was used to track the evolution of the Se valence state for both crystalline and noncrystalline phases, including amorphous and electrolyte-dissolved phases in the (de)lithiation process. On the basis of these results, a mechanism for the (de)lithiation process is proposed, where Se is reduced to the polyselenides, Li2Sen (n ≥ 4), Li2Se2, and Li2Se sequentially during the lithiation and Li2Se is oxidized to Se through Li2Sen (n ≥ 4) during the delithiation. In addition, X-ray photoelectron spectroscopy and electrochemical impedance spectroscopy demonstrated the reversibility of the Li/Se system in ether-based electrolyte and the presence of side products in the carbonate-based electrolytes. For Li/SeS2 and Li/SeS7 cells, Li2Se and Li2S are the discharged products with the presence of Se only as the crystalline phase in the end of charge.

Lack of ferromagnetism in n-type cobalt-doped ZnO epitaxial thin films

Epitaxial thin films of cobalt-doped ZnO (Co : ZnO) were deposited by pulsed laser deposition (PLD) on both c-plane and r-plane sapphire (Al2 O3). The films exhibited high structural quality with narrow x-ray diffraction (XRD) rocking curve peak widths. X-ray absorption spectroscopy (XANES and EXAFS) confirmed well-ordered Co substitution for Zn in ZnO without the formation of secondary phases. A wide range of n-type conductivities (10−4–105 Ω cm) was achieved by controlling the deposition conditions, post-annealing in vacuum, and/or addition of Al during deposition. Despite the high structural quality of the Co : ZnO thin films, no significant room temperature ferromagnetism was observed under any processing or treatment conditions. The lack of ferromagnetism indicates that itinerant conduction band electrons alone are not sufficient to induce ferromagnetism in Co : ZnO, even when the carrier concentration is a significant fraction of the magnetic dopant concentration. The implications of this observation are discussed.

Advanced spectroscopic synchrotron techniques to unravel the intrinsic properties of dilute magnetic oxides: the case of Co:ZnO

The use of synchrotron-based spectroscopy has revolutionized the way we look at matter. X-ray absorption spectroscopy (XAS) using linear and circular polarized light offers a powerful toolbox of element-specific structural, electronic and magnetic probes that is especially well suited for complex materials containing several elements. We use the specific example of Zn1−xCoxO (Co:ZnO) to demonstrate the usefulness of combining these XAS techniques to unravel its intrinsic properties. We demonstrate that as long as phase separation or excessive defect formation is absent, Co:ZnO is paramagnetic. We can establish quantitative thresholds based on four reliable quality indicators using XAS; samples that show ferromagnet-like behaviour fail to meet these quality indicators, and complementary experimental techniques indeed prove phase separation. Careful analysis of XAS spectra is shown to provide quantitative information on the presence and type of dilute secondary phases in a highly sensitive, non-destructive manner.

Kinetics of Reduction of Fe(III) Complexes by Outer Membrane Cytochromes MtrC and OmcA of Shewanella oneidensis MR-1

ABSTRACT Because of their cell surface locations, the outer membrane c-type cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 have been suggested to be the terminal reductases for a range of redox-reactive metals that form poorly soluble solids or that do not readily cross the outer membrane. In this work, we determined the kinetics of reduction of a series of Fe(III) complexes with citrate, nitrilotriacetic acid (NTA), and EDTA by MtrC and OmcA using a stopped-flow technique in combination with theoretical computation methods. Stopped-flow kinetic data showed that the reaction proceeded in two stages, a fast stage that was completed in less than 1 s, followed by a second, relatively slower stage. For a given complex, electron transfer by MtrC was faster than that by OmcA. For a given cytochrome, the reaction was completed in the order Fe-EDTA > Fe-NTA > Fe-citrate. The kinetic data could be modeled by two parallel second-order bimolecular redox reactions with second-order rate constants ranging from 0.872 μM−1 s−1 for the reaction between MtrC and the Fe-EDTA complex to 0.012 μM−1 s−1 for the reaction between OmcA and Fe-citrate. The biphasic reaction kinetics was attributed to redox potential differences among the heme groups or redox site heterogeneity within the cytochromes. The results of redox potential and reorganization energy calculations showed that the reaction rate was influenced mostly by the relatively large reorganization energy. The results demonstrate that ligand complexation plays an important role in microbial dissimilatory reduction and mineral transformation of iron, as well as other redox-sensitive metal species in nature.

Flourescence detection of surface exafs

Abstract The possibilities for flourescence detection of surface EXAFS are studied using thin films of gold on various substrates. For glancing incidence angles it is found that excellent signal to noise ratios can be obtained even for submonolayer films, demonstrating that the technique should have wide applicability to surface and near surface systems. In many cases the signal to noise is superior to electron detection techniques, and its sensitivity suggests the method may also be useful for detection of trace elements on surfaces.

Cr-doped TiO2 anatase: A ferromagnetic insulator

Epitaxial ferromagnetic films of Cr-doped TiO2 anatase (CrxTi1−xO2−x∕2) were grown on LaAlO3(001) using oxygen-plasma-assisted molecular-beam epitaxy. CrK-shell x-ray absorption near-edge spectroscopy shows that the formal oxidation state of Cr is +3 throughout the films, with no evidence for either elemental Cr or half-metallic CrO2. Cr is found to substitute for Ti in the lattice, with uniform distribution throughout the doped region of the film. The Cr-doped anatase films exhibit room-temperature ferromagnetism aligned in-plane, with a saturation magnetization of ∼0.6μB/Cr atom.

Structural parameter determination in fluorescence EXAFS of concentrated samples

Fluorescence detection is often used to obtain the extended x‐ray absorption fine structure (EXAFS) of dilute samples and thin films. As the samples become concentrated and the films become thick, significant errors can be introduced in the EXAFS amplitudes. With detailed calculations we determine the reduction in the coordination numbers (N) and the deviation in the mean‐squared relative displacements (σ2) as determined by fluorescence detection. Experimental results on Cu, Ni, Fe, and Nb samples support the predictions of the calculation. We suggest corrections to obtain the correct coordination numbers and σ2 values for studies of concentrated samples by fluorescence EXAFS detection when other methods are not feasible.

Synthesis and properties of titanomagnetite (Fe3-xTixO4) nanoparticles: A tunable solid-state Fe(II/III) redox system

Titanomagnetite (Fe(3-x)Ti(x)O(4)) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0≤x≤0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. μ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x≤0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.