Experimental probing of the anisotropy of the empty p states near the Fermi level in MgB2

We have studied the Boron K-edge in the superconductor MgB2 by electron energy loss spectroscopy (EELS) and experimentally resolved the empty p states at the Fermi level that have previously been observed within an energy window of 0.8eV by soft x-ray absorption spectroscopy. Using angular resolved EELS, we find that these states at the immediate edge onset have pxy character in agreement with predictions from first-principle electronic structure calculations.Comment: 15 pages, 5 figure

Local boron doping quantification in homoepitaxial diamond structures

The capability of transmission electronmicroscopy (TEM) using the high angle annular dark fieldmode (HAADF,also labelled Z-contrast) to quantify boron concentration, in the high doping range between 1019cm−3 and 1021cm−3, is demonstrated. Thanks to the large relative variation of atomic number Z between carbon and boron, doping concentration maps and profiles are obtained with a nanometer-scale resolution. A novel numerical simulation procedure allows the boron concentration quantification and demonstrates the high sensitivity and spatial resolution of the technique.4 page

Direct observation of nm-scale Mg- and B-oxide phases at grain boundaries in MgB2

Here we describe the results of an atomic resolution study of the structure and composition of both the interior of the grains, and the grain boundaries in polycrystalline MgB2. We find that there is no oxygen within the bulk of the grains but significant oxygen enrichment at the grain boundaries. The majority of grain boundaries contain BOx phases smaller than the coherence length, while others contain larger areas of MgO sandwiched between BOx layers. Such results naturally explain the differences in connectivity between the grains observed by other techniques

Direct measurement of the low-temperature spin-state transition in LaCoO3

LaCoO(3) exhibits an anomaly in its magnetic susceptibility around 80 K associated with a thermally excited transition of the Co(3+)-ion spin. We show that electron energy-loss spectroscopy is sensitive to this Co(3+)-ion spin-state transition, and that the O K edge prepeak provides a direct measure of the Co(3+) spin state in LaCoO(3) as a function of temperature. Our experimental results are confirmed by first-principles calculations, and we conclude that the thermally excited spin-state transition occurs from a low to an intermediate spin state, which can be distinguished from the high-spin state

Inversion of two-band superconductivity at the critical electron doping of (Mg,Al)B-2

Electron energy-loss spectroscopy (EELS) was combined with heat capacity measurements to probe changes of electronic structure and superconductivity in Mg(1-x)AlxB2. A simultaneous decrease of EELS intensity from sigma-band hole states and the magnitude of the sigma gap was observed with increasing x, thus verifying that band filling results in the loss of strong superconductivity. These quantities extrapolated to zero at x approximate to 0.33 as inferred from the unit cell volume. However, superconductivity was not quenched completely, but persisted with T-c< 7 K up to about x approximate to 55. Only the pi band had detectable density of states for 0.33 less than or similar to x less than or similar to 0.55, implying an inversion of the two-band hierarchy of MgB2 in that regime. Since pi-band superconductivity is active in other materials such as intercalated graphite, implications for new materials with high T-c are discussed

Observation of coherent oxide precipitates in polycrystalline MgB2

Here we describe the results of an atomic resolution study of oxygen incorporation into bulk MgB2. We find that ~20-100 nm sized precipitates are formed by ordered substitution of oxygen atoms onto boron lattice sites, while the basic bulk MgB2 crystal structure and orientation is preserved. The periodicity of the oxygen ordering is dictated by the oxygen concentration in the precipitates and primarily occurs in the (010) plane. The presence of these precipitates correlates well with an improved critical current density and superconducting transition behavior, implying that they act as pinning centers.Comment: Submitted to Applied Physics Letters, 6 pages, 3 figure

Giant two-phonon Raman scattering from nanoscale NbC precipitates in Nb

High purity niobium (Nb), subjected to the processing methods used in the fabrication of superconducting RF cavities, displays micron-sized surface patches containing excess carbon. High-resolution transmission electron microscopy and electron energy-loss spectroscopy measurements are presented which reveal the presence of nanoscale NbC coherent precipitates in such regions. Raman backscatter spectroscopy on similar surface regions exhibit spectra consistent with the literature results on bulk NbC but with significantly enhanced two-phonon scattering. The unprecedented strength and sharpness of the two-phonon signal has prompted a theoretical analysis, using density functional theory (DFT), of phonon modes in NbC for two different interface models of the coherent precipitate. One model leads to overall compressive strain and a comparison to ab-initio calculations of phonon dispersion curves under uniform compression of the NbC shows that the measured two-phonon peaks are linked directly to phonon anomalies arising from strong electron-phonon interaction. Another model of the extended interface between Nb and NbC, studied by DFT, gives insight into the frequency shifts of the acoustic and optical mode density of states measured by first order Raman. The exact origin of the stronger two-phonon response is not known at present but it suggests the possibility of enhanced electron-phonon coupling in transition metal carbides under strain found either in the bulk NbC inclusions or at their interfaces with Nb metal. Preliminary tunneling studies using a point contact method show some energy gaps larger than expected for bulk NbC.Comment: Phys. Rev. B, accepte

Aluminum Oxide Layers as Possible Components for Layered Tunnel Barriers

We have studied transport properties of Nb/Al/AlOx/Nb tunnel junctions with ultrathin aluminum oxide layers formed by (i) thermal oxidation and (ii) plasma oxidation, before and after rapid thermal post-annealing of the completed structures at temperatures up to 550 deg C. Post-annealing at temperatures above 300 deg C results in a significant decrease of the tunneling conductance of thermally-grown barriers, while plasma-grown barriers start to change only at annealing temperatures above 450 deg C. Fitting the experimental I-V curves of the junctions using the results of the microscopic theory of direct tunneling shows that the annealing of thermally-grown oxides at temperatures above 300 deg C results in a substantial increase of their average tunnel barriers height, from ~1.8 eV to ~2.45 eV, versus the practically unchanged height of ~2.0 eV for plasma-grown layers. This difference, together with high endurance of annealed barriers under electric stress (breakdown field above 10 MV/cm) may enable all-AlOx and SiO2/AlOx layered "crested" barriers for advanced floating-gate memory applications.Comment: 7 pages, 6 figure

Electron doping in MgB2 studied by electron energy-loss spectroscopy

The electronic structure of electron-doped polycrystalline Mg1-xAlx(B1-yCy)(2) was examined by electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM) and first-principle electronic structure calculations. We found significant changes in the boron K edge fine structure, suggesting the two bands of the B K edge, the sigma and the pi band, are being simultaneously filled as the electron doping concentration of Mg1-xAlx(B1-yCy)(2) was increased. Our density-functional theory calculations confirm the filling of the sigma band states close to the Fermi level, which is believed to cause the loss of superconductivity in highly doped MgB2, since the electron-phonon coupling of these states is thought to be responsible for the high superconducting transition temperature. Our results do not show significant differences in the electronic structure for electron doping on either the Mg or the B site, although many superconducting properties, such as T-c or H-c2 differ considerably for C- and Al-doped MgB2. This behavior cannot be satisfactorily explained by band filling alone, and effects such as interband scattering are considered