Stabilization of metal ensembles at room temperature. Palladium clusters in zeolites

Palladium clusters of low nuclearity have been prepared in the cavities of X zeolites via ion exchange with Pd(NH,),Cl,, oxidative dehydration, and subsequent reduction of the dry Pd(I1) zeolites with hydrogen at 295 and 425 K. Detailed EXAFS analysis of Pd K-edge data shows that the average first-shell Pd-Pd coordination number of the reduced system is only about N = 1.5 at a distance of 2.78 A. A long, relatively disordered coordination of the reduced Pd to framework oxygen and silicon indicates the stabilizing, templating function of the zeolite matrix. Geometric models based upon the EXAFS results show that intrazeolite Pdz, Pd,, and Pd4 clusters are formed by partial occupation of SI and SII positions of the sodalite subunits of the zeolite. This study presents evidence for the formation of molecular metal ensembles stabilized in an open-framework matrix to at least 425 K

Influence of chemical and magnetic interface properties of Co-Fe-B / MgO / Co-Fe-B tunnel junctions on the annealing temperature dependence of the magnetoresistance

The knowledge of chemical and magnetic conditions at the Co40Fe40B20 / MgO interface is important to interpret the strong annealing temperature dependence of tunnel magnetoresistance of Co-Fe-B / MgO / Co-Fe-B magnetic tunnel junctions, which increases with annealing temperature from 20% after annealing at 200C up to a maximum value of 112% after annealing at 350C. While the well defined nearest neighbor ordering indicating crystallinity of the MgO barrier does not change by the annealing, a small amount of interfacial Fe-O at the lower Co-Fe-B / MgO interface is found in the as grown samples, which is completely reduced after annealing at 275C. This is accompanied by a simultaneous increase of the Fe magnetic moment and the tunnel magnetoresistance. However, the TMR of the MgO based junctions increases further for higher annealing temperature which can not be caused by Fe-O reduction. The occurrence of an x-ray absorption near-edge structure above the Fe and Co L-edges after annealing at 350C indicates the recrystallization of the Co-Fe-B electrode. This is prerequisite for coherent tunneling and has been suggested to be responsible for the further increase of the TMR above 275C. Simultaneously, the B concentration in the Co-Fe-B decreases with increasing annealing temperature, at least some of the B diffuses towards or into the MgO barrier and forms a B2O3 oxide

Simultaneous Surface Plasmon Resonance and X-ray Absorption Spectroscopy

We present here an experimental set-up to perform simultaneously measurements of surface plasmon resonance (SPR) and X-ray absorption spectroscopy (XAS) in a synchrotron beamline. The system allows measuring in situ and in real time the effect of X-ray irradiation on the SPR curves to explore the interaction of X-rays with matter. It is also possible to record XAS spectra while exciting SPR in order to detect the changes in the electronic configuration of thin films induced by the excitation of surface plasmons. Combined experiments recording simultaneously SPR and XAS curves while scanning different parameters can be carried out. The relative variations in the SPR and XAS spectra that can be detected with this set-up ranges from 10-3 to 10-5, depending on the particular experiment

Electronic structure studies of Fe- ZnO nanorods by x-ray absorption fine structure

We report the electronic structure studies of well characterized polycrystalline Zn_{1-x}Fe_xO (x = 0.0, 0.01, 0.03, and 0.05) nanorods synthesized by a co-precipitation method through x-ray absorption fine structure (XAFS). X-ray diffraction (XRD) reveals that Fe doped ZnO crystallizes in a single phase wurtzite structure without any secondary phase. From the XRD pattern, it is observed that peak positions shift towards lower 2\theta value with Fe doping. The change in the peak positions with increase in Fe contents clearly indicates that Fe ions are replacing Zn ions in the ZnO matrix. Linear combination fittings (LCF) at Fe K-edge demonstrate that Fe is in mixed valent state (Fe3+/Fe2+) with a ratio of ~ 7:3 (Fe3+:Fe2+). XAFS data is successfully fitted to wurtzite structure using IFEFFIT and Artemis. The results indicate that Fe substitutes Zn site in the ZnO matrix in tetrahedral symmetry.Comment: 7 pages, 5 figures, 2 tables, regular articl

Isochronal annealing effects on local structure, crystalline fraction, and undamaged region size of radiation damage in Ga-stabilized δ\delta-Pu

The effects on the local structure due to self-irradiation damage of Ga stabilized $\delta$-Pu stored at cryogenic temperatures have been examined using extended x-ray absorption fine structure (EXAFS) experiments. Extensive damage, seen as a loss of local order, was evident after 72 days of storage below 15 K. The effect was observed from both the Pu and Ga sites, although less pronounced around Ga. Isochronal annealing was performed on this sample to study the annealing processes that occur between cryogenic and room temperature storage conditions, where damage is mostly reversed. Damage fractions at various points along the annealing curve have been determined using an amplitude-ratio method, standard EXAFS fitting, and a spherical crystallite model, and provide information complementary to previous electrical resistivity- and susceptibility-based isochronal annealing studies. The use of a spherical crystallite model accounts for the changes in EXAFS spectra using just two parameters, namely, the crystalline fraction and the particle radius. Together, these results are discussed in terms of changes to the local structure around Ga and Pu throughout the annealing process and highlight the unusual role of Ga in the behavior of the lowest temperature anneals.Comment: 13 pages, 10 figure

X-ray absorption spectroscopy elucidates the impact of structural disorder on electron mobility in amorphous zinc-tin-oxide thin films

We investigate the correlation between the atomic structures of amorphous zinc-tin-oxide (a-ZTO) thin films grown by atomic layer deposition (ALD) and their electronic transport properties. We perform synchrotron-based X-ray absorption spectroscopy at the K-edges of Zn and Sn with varying [Zn]/[Sn] compositions in a-ZTO thin films. In extended X-ray absorption fine structure (EXAFS) measurements, signal attenuation from higher-order shells confirms the amorphous structure of a-ZTO thin films. Both quantitative EXAFS modeling and X-ray absorption near edge spectroscopy (XANES) reveal that structural disorder around Zn atoms increases with increasing [Sn]. Field- and Hall-effect mobilities are observed to decrease with increasing structural disorder around Zn atoms, suggesting that the degradation in electron mobility may be correlated with structural changes.United States. Office of Naval Research (ONR N00014-10-1-0937)National Science Foundation (U.S.) (Award CBET-1032955)National Science Foundation (U.S.) (CAREER Award ECCS-1150878