No Arabic abstract
The local structure and electronic properties of Rb$_{1-x}$Fe$_{2-y}$Se$_2$ are investigated by means of site selective polarized x-ray absorption spectroscopy at the iron and selenium K-edges as a function of pressure. A combination of dispersive geometry and novel nanodiamond anvil pressure-cell has permitted to reveal a step-like decrease in the Fe-Se bond distance at $psimeq11$ GPa. The position of the Fe K-edge pre-peak, which is directly related to the position of the chemical potential, remains nearly constant until $sim6$ GPa, followed by an increase until $psimeq 11$ GPa. Here, as in the local structure, a step-like decrease of the chemical potential is seen. Thus, the present results provide compelling evidence that the origin of the reemerging superconductivity in $A_{1-x}$Fe$_{2-y}$Se$_2$ in vicinity of a quantum critical transition is caused mainly by the changes in the electronic structure.
We elucidate the termination surface of cleaved single crystals of the BaFe_(2-x)Co_(x)As_(2) and Fe_(y)Se_(1-x)Te_(x) families of the high temperature iron based superconductors. By combining scanning tunneling microscopic data with low energy electron diffraction we prove that the termination layer of the Ba122 systems is a remnant of the Ba layer, which exhibits a complex diversity of ordered and disordered structures. The observed surface topographies and their accompanying superstructure reflections in electron diffraction depend on the cleavage temperature. In stark contrast, Fe_(y)Se_(1-x)Te_(x) possesses only a single termination structure - that of the tetragonally ordered Se_(1-x)Te_(x) layer.
From low-temperature Synchrotron X-ray diffraction, a precise thermal characterization of octahedral distortions in single phase Ruddlesden-Popper Ca3Mn2O7 is performed. Highly sensitive close-steps temperature dependences of Mn-O-Mn bond angles connecting MnO6 octahedra clearly reveal signature of the spin-ordering in the system. Spin-lattice coupling is thus established via the structural distortions responsible for evolution of the magnetic state. Further, temperature anomalies observed here in volume and polarization-measure of the unit cell highlight the interplay between spin, lattice and charge degrees of freedom. Dipole-relaxation characteristics examined under applied magnetic field consistently corroborate the concurrent magnetic and structural changes, in terms of genuine and intrinsic magneto-dielectricity.
We report the synthesis and superconducting properties of a metastable form of the known superconductor NaxCoO2*yH2O (x ~ 1/3, y ~ 4x). Instead of using the conventional bromine-acetonitrile mixture for sodium deintercalation, we use an aqueous bromine solution. Using this method, we oxidize the sample to a point that the sodium cobaltate becomes unstable, leading to formation of other products if not controlled. This compound has the same structure as the reported superconductor, yet it exhibits a systematic variation of the superconducting transition temperature (Tc) as a function of time. Immediately after synthesis, this compound is not a superconductor, even though it contains appropriate amounts of sodium and water. The samples become superconducting with low Tc values after ~ 90 h. Tc continually increases until it reaches a maximum value (4.5 K) after about 260 h. Then Tc drops drastically, becoming non-superconducting approximately 100 h later. Corresponding time-dependent neutron powder diffraction data shows that the changes in superconductivity exhibited by the metastable cobaltate correspond to slow formation of oxygen vacancies in the CoO2 layers. In effect, the formation of these defects continually reduces the cobalt oxidation state causing the sample to evolve through its superconducting life cycle. Thus, the dome-shaped superconducting phase diagram is mapped as a function of cobalt oxidation state using a single sample. The width of this dome based on the formal oxidation state of cobalt is very narrow - approximately 0.1 valence units wide. Interestingly, the maximum Tc in NaxCoO2*yH2O occurs when the cobalt oxidation state is near 3.5. Thus, we speculate that the maximum Tc occurs near the charge ordered insulating state that correlates with the average cobalt oxidation state of 3.5.
The electronic and magnetic properties of a new diluted magnetic semiconductor (DMS) Ba$_{1-x}$K$_{x}$(Zn$_{1-y}$Mn$_{y}$)$_{2}$As$_{2}$, which is isostructural to so-called 122-type Fe-based superconductors, are investigated by x-ray absorption spectroscopy (XAS) and resonance photoemission spectroscopy (RPES). Mn $L_{2,3}$-edge XAS indicates that the doped Mn atoms have the valence 2+ and strongly hybridize with the $4p$ orbitals of the tetrahedrally coordinating As ligands. The Mn $3d$ partial density of states (PDOS) obtained by RPES shows a peak around 4 eV and relatively high between 0-2 eV below the Fermi level ($E_{F}$) with little contribution at $E_{F}$, similar to that of the archetypal DMS Ga$_{1-x}$Mn$_{x}$As. This energy level creates $d^{5}$ electron configuration with $S=5/2$ local magnetic moments at the Mn atoms. Hole carriers induced by K substitution for Ba atoms go into the top of the As $4p$ valence band and are weakly bound to the Mn local spins. The ferromagnetic correlation between the local spins mediated by the hole carriers induces ferromagnetism in Ba$_{1-x}$K$_{x}$(Zn$_{1-y}$Mn$_{y}$)$_{2}$As$_{2}$
We probed the local electronic properties of the mixed-valent Co(+4-x) triangular-lattice in Na{x}CoO{2}-yH{2}O by 59-Co NMR. We observed two distinct types of Co sites for x>=1/2, but the valence seems averaged out for x~1/3. Local spin fluctuations exhibit qualitatively the same trend down to ~100 K regardless of the carrier-concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below ~100 K only for x~1/3.