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Register a new userBulk Electronic structure of Na$_{0.35}$CoO$_{2}$.1.3H$_{2}$O
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High-energy (h$ u$ = 5.95 keV) synchrotron Photoemission spectroscopy (PES) is used to study bulk electronic structure of Na$_{0.35}$CoO$_{2}$.1.3H$_{2}$O, the layered superconductor. In contrast to 3-dimensional doped Co oxides, Co $it{2p}$ core level spectra show well-separated Co$^{3+}$ and Co$^{4+}$ ions. Cluster calculations suggest low spin Co$^{3+}$ and Co$^{4+}$ character, and a moderate on-site Coulomb correlation energy U$_{dd}sim$3-5.5 eV. Photon dependent valence band PES identifies Co $it{3d}$ and O $it{2p}$ derived states, in near agreement with band structure calculations.
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In order to investigate the role of the water molecules in Na$_{0.35}$CoO$_{2}cdot$1.3H$_{2}$O, we synthesized superconducting Na$_{0.35}$CoO$_{2}cdot$1.3H$_{2}$O and nonsuperconducting Na$_{0.35}$CoO$_{2}cdot$0.7H$_{2}$O, and measured their normal-state magnetic susceptibilities. The susceptibility of Na$_{0.35}$CoO$_{2}cdot$1.3H$_{2}$O has an enhancement below ~150 K probably caused by ferromagnetic fluctuation, whereas no such enhancement was observed in Na$_{0.35}$CoO$_{2}cdot$0.7H$_{2}$O. The water molecules in Na$_{0.35}$CoO$_{2}cdot$1.3H$_{2}$O may work to shield random coulomb potential of the Na ions with smoother potential at the CoO$_{2}$ layer. This effect may account for the appearance of superconductivity in Na$_{0.35}$CoO$_{2}cdot$1.3H$_{2}$O.
The idea that surface effects may play an important role in suppressing $e_g$ Fermi surface pockets on Na$_x$CoO$_2$ $(0.333 le x le 0.75)$ has been frequently proposed to explain the discrepancy between LDA calculations (performed on the bulk compound) which find $e_g$ hole pockets present and ARPES experiments, which do not observe the hole pockets. Since ARPES is a surface sensitive technique it is important to investigate the effects that surface formation will have on the electronic structure of Na$_{1/3}$CoO$_2$ in order to more accurately compare theory and experiment. We have calculated the band structure and Fermi surface of cleaved Na$_{1/3}$CoO$_2$ and determined that the surface non-trivially affects the fermiology in comparison to the bulk. Additionally, we examine the likelihood of possible hydroxyl cotamination and surface termination. Our results show that a combination of surface formation and contamination effects could resolve the ongoing controversy between ARPES experiments and theory.
We have synthesized various samples of the $x=2/3$ phase of sodium cobaltate Na$_{x}$CoO$_{2}$ and performed X-ray powder diffractions spectra to compare the diffraction with the structure proposed previously from NMR/NQR experiments [H. Alloul emph{et al.}, EPL textbf{85}, 47006 (2009)]. Rietveld analysis of the data are found in perfect agreement with those, and confirm the concentration x=2/3 obtained in the synthesis procedure. They even give indications on the atomic displacements of Na inside the unit cell. The detailed NQR data allow us to identify the NQR transitions and electric field gradient (EFG) parameters for 4 cobalt sites and 3 Na sites. The spin-lattice and spin-spin relaxation rates are found much smaller for the non-magnetic Co$^{3+}$ sites than for the magnetic sites on which the holes are delocalized. The atomic ordering of the Na layers is therefore at the source of this ordered distribution of cobalt charges. The method used here to resolve the Na ordering and the subsequent Co charge order can be used valuably for other concentrations of Na.
We have used electron and neutron powder diffraction to elucidate the structural properties of superconducting NaD. Our measurements show that our superconducting sample exhbits a number of supercells ranging from ${1/3}a^{*}$ to ${1/15}a^{*}$, but the most predominant one, observed also in the neutron data, is a double hexagonal cell with dimensions dhx. Rietveld analysis reveals that deutspace is inserted between CoO$_{2}$ sheets as to form a layered network of NaO$_{6}$ triangular prisms. Our model removes the need to invoke a 5K superconducting point compound and suggests that a solid solution of Na is possible within a constant amount of water $y$.
We report the in-plane resistivity and magnetic susceptibility of the layered cobalt oxide Na$_{0.35}$CoO$_{2}{cdot}1.3$H$_{2}$O single crystal. The temperature dependence of the resistivity shows metallic behavior from room temperature to the superconducting transition temperature $T_{c}$ of 4.5 K. Sharp resistive transition, zero resistivity and almost perfect superconducting volume fraction below $T_{c}$ indicate the good quality and the bulk superconductivity of the single crystal. The upper critical field $H_{c2}$ and the coherence length $xi$ are obtained from the resistive transitions in magnetic field parallel to the c-axis and the $ab$-plane. The anisotropy of $xi$, $xi_{ab} / xi_{c} =$ 12 nm/1.3 nm $simeq$ 9.2, suggests that this material is considered to be an anisotropic three dimensional superconductor. In the field parallel to the $ab$-plane, $H_{c2}$ seems to be suppressed to the value of Pauli paramagnetic limit. It may indicate the spin singlet superconductivity in the cobalt oxide.
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