Novel phase diagram of superconductor NaxCoO2-yH2O in a 75 % relative humidity

We succeeded in synthesizing the powder samples of bilayer-hydrate sodium cobalt oxide superconductors NaxCoO2-yH2O with Tc = 0 ~ 4.6 K by systematically changing the keeping duration in a 75 % relative humidity atmosphere after intercalation of water molecules. From the magnetic measurements, we found that the one-day duration sample does not show any superconductivity down to 1.8 K, and that the samples kept for 2 ~ 7 days show superconductivity, in which Tc increases up to 4.6 K with increasing the duration. Tc and the superconducting volume fraction are almost invariant between 7 days and 1month duration. The 59Co NQR spectra indicate a systematic change in the local charge distribution on the CoO2 plane with change in duration.Comment: 4 pages, 5 figures, submitted to Journal of the Physical Society of Japa

Correlation between Superconducting Transition Temperature TcT_c and Increase of Nuclear Spin-Lattice Relaxation Rate Devided by Temperature 1/T1T1/T_1T at TcT_c in the Hydrate Cobaltate Nax_{x}CoO2⋅y_{2}\cdot yH2_{2}O

We have performed Co-nuclear quadrupole resonance (NQR) studies on Na$_{x}$CoO$_{2}\cdot y$H$_{2}$O compounds with different Na ($x$) and hydrate ($y$) contents. Two samples with different Na contents but nearly the same $T_c$ values ($x$ = 0.348, $T_c$ = 4.7 K ; $x$ = 0.339, $T_c$ = 4.6 K) were investigated. The spin-lattice relaxation rate $1/T_1$ in the superconducting (SC) and normal states is almost the same for the two samples except just above $T_c$. NQR measurements were also performed on different-hydrate-content samples with different $T_c$ values, which were prepared from the same Na-content ($x$ = 0.348) sample. From measurements of $1/T_1$ using the different-hydrate-content samples, it was found that a low-$T_c$ sample with $T_c = 3.9$ K has a larger residual density of states (DOS) in the SC state and a smaller increase of $1/T_1T$ just above $T_c$ than a high-$T_c$ sample with $T_c$ = 4.7 K. The former behavior is consistent with that observed in unconventional superconductors, and the latter suggests the relationship between $T_c$ and the increase in DOS just above $T_c$. This increase, which is seemingly associated with the two-dimensionality of the CoO$_2$ plane, is considered to be one of the most important factors for the occurrence of superconductivity.Comment: 5 pages, 5 figures, To be published in J. Phys. Soc. Jp

Structure and Dynamics of Superconducting NaxCoO(2) Hydrate and Its Unhydrated Analog

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 refere

Unconventional Superconductivity and Nearly Ferromagnetic Spin Fluctuations in Nax_xCoO2_2⋅y\cdot yH2_2O

Co NQR studies were performed in recently discovered superconductor Na$_x$CoO$_2$$\cdot y$H$_2$O to investigate physical properties in the superconducting (SC) and normal states. Two samples from the same Na$_x$CoO$_2$ were examined, SC bilayer-hydrate sample with $T_c \sim 4.7$ K and non-SC monolayer-hydrate sample. From the measurement of nuclear-spin lattice relaxation rate $1/T_1$ in the SC sample, it was found that the coherence peak is absent just below $T_c$ and that $1/T_1$ is proportional to temperature far below $T_c$. These results, which are in qualitatively agreement with the previous result by Fujimoto {\it et al.}, suggest strongly that unconventional superconductivity is realized in this compound. In the normal state, $1/T_1T$ of the SC sample shows gradual increase below 100K down to $T_c$, whereas $1/T_1T$ of the non-SC sample shows the Korringa behavior in this temperature range. From the comparison between $1/T_1T$ and $\chi_{\rm bulk}$ in the SC sample, the increase of $1/T_1T$ is attributed to nearly ferromagnetic fluctuations. These remarkable findings suggest that the SC sample possesses nearly ferromagnetic fluctuations, which are possibly related with the unconventional superconductivity in this compound. The implication of this finding is discussed.Comment: 4 pages, 5 figures. submitted to J. Phys. Soc. Jp

Novel Synthesis and High Pressure Behavior of Na0.3CoO2 x 1.3 H2O and Related Phases

We have prepared powder samples of NaxCoO2 x yH2O using a new synthesis route. Superconductivity was observed in Na0.3CoO2 x 1.3H2O between 4 and 5K as indicated by the magnetic susceptibility. The bulk compressibilities of Na0.3CoO2 x 1.3H2O, Na0.3CoO2 x 0.6H2O and Na0.3CoO2 were determined using a diamond anvil cell and synchrotron powder diffraction. Chemical changes occurring under pressure when using different pressure transmitting media are discussed and further transport measurements are advocated.Comment: 7 pages, 4 figures, PRrapid submitte

Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction

Nanoparticles of nickel phosphide (Ni_2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni_2P nanoparticles were hollow and faceted to expose a high density of the Ni_2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H_2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media

Electrocatalytic hydrogen evolution using amorphous tungsten phosphide nanoparticles

Amorphous tungsten phosphide (WP), which has been synthesized as colloidal nanoparticles with an average diameter of 3 nm, has been identified as a new electrocatalyst for the hydrogen-evolution reaction (HER) in acidic aqueous solutions. WP/Ti electrodes produced current densities of −10 mA cm^(−2) and −20 mA cm^(−2) at overpotentials of only −120 mV and −140 mV, respectively, in 0.50 M H_2SO_4(aq)

Quasiparticle vanishing driven by geometrical frustration

We investigate the single hole dynamics in the triangular t-J model. We study the structure of the hole spectral function, assuming the existence of a 120 magnetic Neel order. Within the self-consistent Born approximation (SCBA) there is a strong momentum and t sign dependence of the spectra, related to the underlying magnetic structure and the particle-hole asymmetry of the model. For positive t, and in the strong coupling regime, we find that the low energy quasiparticle excitations vanish outside the neighbourhood of the magnetic Goldstone modes; while for negative t the quasiparticle excitations are always well defined. In the latter, we also find resonances of magnetic origin whose energies scale as (J/t)^2/3 and can be identified with string excitations. We argue that this complex structure of the spectra is due to the subtle interplay between magnon-assisted and free hopping mechanisms. Our predictions are supported by an excellent agreement between the SCBA and the exact results on finite size clusters. We conclude that the conventional quasiparticle picture can be broken by the effect of geometrical magnetic frustration.Comment: 6 pages, 7 figures. Published versio

Deformation of Electronic Structures Due to CoO6 Distortion and Phase Diagrams of NaxCoO2.yH2O

Motivated by recently reported experimental phase diagrams, we study the effects of CoO6 distortion on the electronic structure in NaxCoO2.yH2O. We construct the multiband tight-binding model by employing the LDA result. Analyzing this model, we show the deformation of band dispersions and Fermi-surface topology as functions of CoO2-layer thickness. Considering these results together with previous theoretical ones, we propose a possible schematic phase diagram with three successive phases: the extended s-wave superconductivity (SC), the magnetic order, and the spin-triplet SC phases when the Co valence number s is +3.4. A phase diagram with only one phase of spin-triplet SC is also proposed for the s=+3.5 case.Comment: 4 pages, 5 figure

Variational Monte Carlo Studies of Pairing Symmetry for the t-J Model on a Triangular Lattice

As a model of a novel superconductor Na_xCoO_2\cdotyH_2O, a single-band t-J model on a triangular lattice is studied, using a variational Monte Carlo method. We calculate the energies of various superconducting (SC) states, changing the doping rate \delta and sign of t for small J/|t|. Symmetries of s, d, and d+id (p+ip and f) waves are taken up as candidates for singlet (triplet) pairing. In addition, the possibility of Nagaoka ferromagnetism and inhomogeneous phases is considered. It is revealed that, among the SC states, the d+id wave always has the lowest energy, which result supports previous mean-field studies. There is no possibility of triplet pairing, although the f-wave state becomes stable against a normal state in a special case (\delta=0.5 and t<0). For t<0, the complete ferromagnetic state is dominant in a wide range of \delta and J/|t|, which covers the realistic parameter region of superconductivity.Comment: 10 pages, 13 figure