Search

We have measured transport properties as a function of temperature and pressure up to 30GPa in the NaxCoO2 system. For the x=0.5 sample the transition temperature at 53K increases with pressure, while paradoxically the sample passes from an insulating to a metallic ground state. A similar transition is observed in the x=0.31 sample under pressure. Compression on the x=0.75 sample transforms the sample from a metallic to an insulating state. We discuss our results in terms of interactions between band structure effects and Na+ order., Comment: 18 pages, 5 figures

Research on the oxide perovskites has uncovered electronic properties that are strikingly enhanced compared with those in conventional metals. Examples are the high critical temperatures of the cuprate superconductors and the colossal magnetoresistance in the manganites. The conducting layered cobaltate $\rm Na_xCoO_2$ displays several interesting electronic phases as $x$ is varied including water-induced superconductivity and an insulating state that is destroyed by field. Initial measurements showed that, in the as-grown composition, $\rm Na_xCoO_2$ displays moderately large thermopower $S$ and conductivity $\sigma$. However, the prospects for thermoelectric cooling applications faded when the figure of merit $Z$ was found to be small at this composition (0.6$$0.75, $S$ undergoes an even steeper enhancement. At the critical doping $x_p\sim$ 0.85, $Z$ (at 80 K) reaches values $\sim$40 times larger than in the as-grown crystals. We discuss prospects for low-temperature thermoelectric applications., Comment: 6 pages, 7 figures

We report detailed Fermi surface topology and quasiparticle dynamics of the host cobaltate Na0.7CoO2. A direct mapping of the Fermi surface is carried out by angle-resolved photoemission spectroscopy (ARPES). Fermi surface at temperature 16K is a hole-pocket centered around the Gamma-point. The highly correlated nature of the electron liquid is evidenced from strong on-site Coulomb interaction seen through a valence satellite and via renormalization of the quasiparticle dispersion. The quasiparticle exhibits spectral coherence only below 150K which includes the non-Fermi liquid regime., Comment: Conference proceeding. SNS-2004, Spain

The crystal structures of the NaxCoO2 phases based on three-layer NaCoO2, with x=0.32, x=0.51, x=0.60, x=0.75 and x=0.92, determined by powder neutron diffraction, are reported. The structures have triangular CoO2 layers interleaved by sodium ions, and evolve with variation in Na content in a more complex way than has been observed in the two-layer NaxCoO2 system. The highest and lowest Na containing phases studied (x=0.92 and x=0.32) are trigonal, with three CoO2 layers per cell and octahedral Na ion coordination. The intermediate compositions have monoclinic structures. The x=0.75 compound has one CoO2 layer per cell, with Na in octahedral coordination and an incommensurate superlattice. The x=0.6 and x=0.5 phases are also single-layer, but the Na is found in trigonal prismatic coordination. The magnetic behavior of the phases is similar to that observed in the two-layer system. Both the susceptibility and the electronic contribution to the specific heat are largest for x=0.6., Comment: 24 pages, 14 figures, submitted to Phys.Rev. B

The structure of Na0.5CoO2, the low temperature insulator that separates the magnetic and superconducting regions in the NaxCoO2.yH2O phase diagram, is studied by high resolution powder neutron diffraction at temperatures between 10 and 300 K. Profile analysis confirms that it has an orthorhombic symmetry structure, space group Pnmm, consisting of layers of edge-sharing CoO6 octahedra in a triangular lattice, with Na ions occupying ordered positions in one-dimensional chains in the interleaving planes. The oxygen content is found to be stoichiometric within 1%, indicating that the Na concentration accurately determines the electronic doping. The Na ordering creates two distinct Co sites with different numbers of Na neighbours, but the difference in their Co-O bond distances and the derived bond valence sums is small., Comment: 16 pages, 3 figures

The specific heats of three samples of Na0.35CoO2,1.3H2O show an evolution of the superconductivity, and its ultimate disappearance, with increasing sample age. An overall increase in pair-breaking action, which occurs preferentially in an electron band with a small energy gap, produces a shift in the relative contributions of two electron bands to the superconducting condensation. The similarity of the time scale for these changes to that recently reported for structural changes in the CoO2 layers and the formation of O vacancies suggests a relation between the two effects and an explanation for the strong sample dependence of the properties of this material more generally. The onset of the transition to the vortex state is independent of magnetic field, suggesting the presence of unusually strong fluctuation effects., Comment: 11 pages, 5 figures

Recently discovered class of cobaltate superconductors (Na0.3CoO2.nH2O) is a novel realization of interacting quantum electron systems in a triangular network with low-energy degrees of freedom. We employ angle-resolved photoemission spectroscopy to uncover the nature of microscopic electron motion in the parent superconductors for the first time. Results reveal a large hole-like Fermi surface (consistent with Luttinger theorem) generated by the crossing of super-heavy quasiparticles. The measured quasiparticle parameters collectively suggest a two orders of magnitude departure from the conventional Bardeen-Cooper-Schrieffer electron dynamics paradigm and unveils cobaltates as a rather hidden class of relatively high temperature superconductors., Comment: 5 pages, 4 figures, 1 table

The hydration phase diagram for sodium cobalt oxyhydrate, Na0.3CoO2*yH2O (y=0, 0.6, 1.3), was determined as a function of relative humidity at 298K. It is found that greater than 75% relative humidity is needed for complete hydration of anhydrous Na0.3CoO2 to the superconducting phase Na0.3CoO2*1.3H2O. Dehydration studies show that a minimum of 43% relative humidity is needed to maintain the stability of the fully hydrated superconducting phase. The intermediate hydrate, Na0.3CoO2*0.6H2O, is stable between 10% and 50% relative humidity on hydration, and 35% to 0% relative humidity on dehydration., Comment: submitted to Mat. Res. Bull., 4 pages, 4 figures

The superconducting-state heat capacity of Na$_{0.3}$CoO$_{2}$$\cdot$1.3H$_{2}$O shows unusual, marked deviations from BCS theory, at all temperatures. At low temperatures the heat capacity has the $T^2$ dependence characteristic of line nodes in the energy gap, rather than the exponential temperature dependence of a fully gapped, conventional superconductor. At temperatures of the order of one fifth of the critical temperature and above, the deviations are strikingly similar to those of MgB$_2$, which are known to be a consequence of the existence of substantially different energy gaps on different sheets of the Fermi surface. A two-gap fit to the Na$_{0.3}$CoO$_{2}$$\cdot$1.3H${_2}$O data gives gap amplitudes of 45% and 125% of the BCS value, on parts of the Fermi surface that contribute, respectively, 45% and 55% to the normal-state density of states. The temperature of the onset of the transition to the vortex state is independent of magnetic field, which shows the presence of unusually strong fluctuations., Comment: to appear in Chinese Journal of Physics

The determination by powder neutron diffraction of the ambient temperature crystal structures of compounds in the NaxCoO2 family, for 0.3 < x <= 1.0, is reported. The structures consist of triangular CoO2 layers with Na ions distributed in intervening charge reservoir layers. The shapes of the CoO6 octahedra that make up the CoO2 layers are found to be critically dependent on the electron count and on the distribution of the Na ions in the intervening layers, where two types of Na sites are available. Correlation of the shapes of cobalt-oxygen octahedra, the Na ion positions, and the electronic phase diagram in NaxCoO2 is made, showing how structural and electronic degrees of freedom can be coupled in electrically conducting triangular lattice systems., Comment: 15 pages, 1 tables, 6 figures Submitted to Physical Review B

The observation of superconductivity at 4.3 K in a new crystalline form of Na0.3CoO2*1.3H2O is reported. The new superconductor has three layers of CoO6 octahedra per crystallographic unit cell, in contrast to the previously reported two-layer superconductor. The three-layer cell occurs because the relative orientations of neighboring CoO2 layers are distinctly different from what is seen in the two-layer superconducting phase. This type of structural difference in materials that are otherwise chemically and structurally identical is not possible to attain on the layered copper oxide superconductors. The synthesis and stability of the new phase are described., Comment: 10 pages, 4 figures. Submitted to Physical Review Letters

The layered sodium cobalt oxide NaxCoO2 is studied by electron diffraction for a wide range of sodium contents, 0.15

Muon spin relaxation ($\mu$SR) measurements on the new layered cobalt oxide superconductor Na$_{0.35}$CoO$_{2}\cdot$1.3H$_{2}$O and its parent, non-superconducting compounds, have revealed unconventional nature of superconductivity through: (1) a small superfluid energy which implies a surprisingly high effective mass of the charge carriers, approximately 100 times the bare electron mass; (2) the superconducting transition temperature $T_{c}$ scaling with the superfluid energy following the correlations found in high-$T_{c}$ cuprate and some other two-dimensional superconductors; (3) an anisotropic pairing without broken time-reversal symmetry; and (4) the proximity of a magnetically ordered insulating phase at Na$_{0.5}$CoO$_{2}$ below $T_{N}$ = 53 K., Comment: 6 pages 4 figures: Contact Y.J. Uemura, E-mail: tomo@lorentz.phys.columbia.edu

We present precise measurements of the upper critical field (Hc2) in the recently discovered cobalt oxide superconductor. We have found that the critical field has an unusual temperature dependence; namely, there is an abrupt change of the slope of Hc2(T) in a weak field regime. In order to explain this result we have derived and solved Gor'kov equations on a triangular lattice. Our experimental results may be interpreted in terms of the field-induced transition from singlet to triplet superconductivity., Comment: 6 pages, 5 figures, revtex

The crystal structure of Na0.5CoO2, determined by powder neutron diffraction, is reported. The structure consists of layers of edge-shared CoO6 octahedra in a triangular lattice, with Na ions occupying ordered positions in the interleaving planes. The Na ions form one-dimensional zigzag chains. Two types of Co ions, which differ only subtly in their coordination by oxygen, are also found in chains. Specific heat measurements show that the transitions observed at 87 K and 53 K in the resistivity and magnetic susceptibility are accompanied by changes in entropy. Electron diffraction studies suggest that the 87K transition may have a structural component., Comment: 19 pages, 10 figures, submitted to Journal of Physics: Condensed Matter. Revised structural parameters on page 7

We present an angle-resolved photoemission study of Na0.7CoO2, the host cobaltate of the NaxCoO2.yH2O series. Our results show a large hexagonal-like hole-type Fermi surface, an extremely narrow strongly renormalized quasiparticle band and a small Fermi velocity. Along the Gamma to M high symmetry line, the quasiparticle band crosses the Fermi level from M toward Gamma consistent with a negative sign of effective single-particle hopping (t ): t is estimated to be about 8 meV which is on the order of exchange coupling J in this system. This suggests that t ~ J ~ 10 meV is an important energy scale in the system. Quasiparticles are well defined only in the T-linear resistivity regime. Small single particle hopping and unconventional quasiparticle dynamics may have implications for understanding the unusual behavior of this new class of compounds., Comment: Revised text, Added Figs, Submitted to PRL

Neutron scattering has been used to investigate the crystal structure and lattice dynamics of superconducting Na0.3CoO2 1.4(H/D)2O, and the parent Na0.3CoO2 material. The structure of Na0.3CoO2 consists of alternate layers of CoO2 and Na and is the same as the structure at higher Na concentrations. For the superconductor, the water forms two additional layers between the Na and CoO2, increasing the c-axis lattice parameter of the hexagonal P63/mmc space group from 11.16 A to 19.5 A. The Na ions are found to occupy a different configuration from the parent compound, while the water forms a structure that replicates the structure of ice. Both types of sites are only partially occupied. The CoO2 layer in these structures is robust, on the other hand, and we find a strong inverse correlation between the CoO2 layer thickness and the superconducting transition temperature (TC increases with decreasing thickness). The phonon density-of-states for Na0.3CoO2 exhibits distinct acoustic and optic bands, with a high-energy cutoff of ~100 meV. The lattice dynamical scattering for the superconductor is dominated by the hydrogen modes, with librational and bending modes that are quite similar to ice, supporting the structural model that the water intercalates and forms ice-like layers in the superconductor., Comment: 14 pages, 7 figures, Phys. Rev. B (in press). Minor changes + two figures removed as requested by referee

We report results of specific heat measurements on polycrystalline samples of the layered superconductor, Na(0.3)CoO(2).1.3H(2)O. The electronic contribution to the specific heat, gamma, is found to be 12.2 mJ/mol-K2. The feature at the superconducting transition is rather sharp, becoming broad and strongly suppressed in an applied magnetic field. The data indicate a residual normal state electronic specific heat at low temperatures, implying that there is a sizable population of normal state electrons in the samples even below Tc. Inhomogeneity in the Na content, to which the superconducting state is exquisitely sensitive, appears to be the most likely explanation for these results. These results further indicate that special sample handling is required for an accurate characterization of the superconducting state in this material., Comment: publication information added

Although the microscopic origin of the superconductivity in high Tc copper oxides remains the subject of active inquiry, several of their electronic characteristics are well established as universal to all the known materials, forming the experimental foundation that all theories must address. The most fundamental of those characteristics is the dependence of the superconducting transition temperature on the degree of electronic band filling. Since the discovery of cuprate superconductivity in 1986 (1), the search for other families of superconductors that might help shed light on the superconducting mechanism of the cuprates has been of great interest. The recent report of superconductivity near 4K in the triangular lattice, layered sodium cobalt oxyhydrate, Na0.35CoO2.1.3H2O, is the best indication that superconductors related to the cuprates may be found (2). Here we show that the superconducting transition temperature of this compound displays the same kind of band-filling behavior that is observed in the cuprates. Specifically, that the optimal superconducting Tc occurs in a narrow range of band filling, and decreases for both underdoped and overdoped materials, in dramatic analogy to the phase diagram of the cuprate superconductors. Our results suggest that characterization of the detailed electronic and magnetic behavior of these new materials may help establish which of the many special characteristics of the cuprates is fundamental to their high Tc superconductivity., Comment: revised, publication information added

The layered sodium cobalt oxyhydrate superconductor Na0.3CoO2*1.4H2O is shown through X-ray diffraction and thermogravimetric studies to be one of a series of hydrated phases of Na0.3CoO2. Further, it is shown that the material is exceptionally sensitive to both temperature and humidity near ambient conditions, easily dehydrating to a non-superconducting lower hydrate. The observation of this stable lower hydrate with c=13.8 angstroms implies that the superconductivity turns on in this system between CoO2 layer spacings of 6.9 and 9.9 angstroms at nominally constant chemical doping., Comment: 10 pages and 4 figures