Charge-ordering, commensurability and metallicity in the phase diagram of layered Na(x)CoO(2)

The phase diagram of non-hydrated Na(x)CoO(2) has been determined by changing the Na content x using a series of chemical reactions. As x increases from 0.3, the ground state goes from a paramagnetic metal to a charge-ordered insulator (at x=1/2) to a `Curie-Weiss metal' (around 0.70), and finally to a weak-moment magnetically ordered state (x>0.75). The unusual properties of the state at 1/2 (including particle-hole symmetry at low T and enhanced thermal conductivity) are described. The strong coupling between the Na ions and the holes is emphasized.Comment: 4 pages with 3 figures, changed conten

Coupling between electronic and structural degrees of freedom in the triangular lattice conductor NaxCoO2

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

Charge order and superconductivity in a two-dimensional triangular lattice at n=2/3

To investigate the possibility of charge order and superconductivity in a doped two-dimensional triangular lattice, we study the extended Hubbard model with variational Monte Carlo method. At n=2/3, a commensurate filling for a triangular lattice, it is shown that the nearest-neighbor Coulomb interaction V induces honeycomb-type charge order and antiferromagnetic spin order at U>10t. We also discuss the possibility of superconductivity induced by charge fluctuation and the relation to the superconductivity in Na_{0.35}CoO_{2}1.3H_{2}O and theta-type organic condoctors.Comment: 4 pages, 5 figure

A novel route to phase formation of cobalt oxyhydrates using KMnO4 as an oxidizing agent

We have first succeefully synthesized the sodium cobalt oxyhydrate superconductors using KMnO4 as a de-intercalating and oxidizing agent. It is a novel route to form the superconductive phase of NaxCoO2.yH2O without resorting to the commonly used Br2/CH3CN solution. The role of the KMnO4 is to de-intercalate the Na+ from the parent compound Na0.7CoO2 and oxidize the Co ion as a result. The higher molar ratio of KMnO4 relative to the sodium content tends to remove more Na+ from the parent compound and results in a slight expansion of the c-axis in the unit cell. The superconducting transition temperature is 4.6-3.8 K for samples treated by the aqueous KMnO4 solution with the molar ratio of KMnO4 relative to the sodium content in the range of 0.3 and 2.29.Comment: 10 pages, 3 figure

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

Phase segregation in NaxCoO2 for large Na contents

We have investigated a set of sodium cobaltates (NaxCoO2) samples with various sodium content (0.67 \le x \le 0.75) using Nuclear Quadrupole Resonance (NQR). The four different stable phases and an intermediate one have been recognized. The NQR spectra of 59Co allowed us to clearly differentiate the pure phase samples which could be easily distinguished from multi-phase samples. Moreover, we have found that keeping samples at room temperature in contact with humid air leads to destruction of the phase purity and loss of sodium content. The high sodium content sample evolves progressively into a mixture of the detected stable phases until it reaches the x=2/3 composition which appears to be the most stable phase in this part of phase diagram.Comment: 5 pages, 4 figure

Fermi surface and quasiparticle dynamics of Na(x)CoO2 {x=0.7} investigated by Angle-Resolved Photoemission Spectroscopy

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 PR

NMR studies of Successive Phase Transitions in Na0.5CoO2 and K0.5CoO2

59Co- and 23Na-NMR measurements have been carried out on polycrystalline and c-axis aligned samples of Na0.5CoO2, which exhibits successive transitions at temperatures T = 87 K (= Tc1) and T = 53 K (= Tc2). 59Co-NMR has also been carried out on c-axis aligned crystallites of K0.5CoO2 with similar successive transitions at Tc1 ~ 60 K and Tc2 ~ 20 K. For Na0.5CoO2, two sets of three NMR lines of 23Na nuclei explained by considering the quadrupolar frequencies nuQ ~1.32 and 1.40 MHz have been observed above Tc1, as is expected from the crystalline structure. Rather complicated but characteristic variation of the 23Na-NMR spectra has been observed with varying T through the transition temperatures, and the internal fields at two crystallographically distinct Na sites are discussed on the basis of the magnetic structures reported previously. The internal fields at two distinct Co sites observed below Tc1 and the 591/T1-T curves of Na0.5CoO2 and K0.5CoO2 are also discussed in a comparative way.Comment: 7 pages, 10 figures, submitted to J. Phys. Soc. Jpn, correction is made in right colum of p6 (35th line) as K0.5CoO2-->Na0.5CoO

Emergence of Anti-Cancer Drug Resistance: Exploring the Importance of the Microenvironmental Niche via a Spatial Model

Practically, all chemotherapeutic agents lead to drug resistance. Clinically, it is a challenge to determine whether resistance arises prior to, or as a result of, cancer therapy. Further, a number of different intracellular and microenvironmental factors have been correlated with the emergence of drug resistance. With the goal of better understanding drug resistance and its connection with the tumor microenvironment, we have developed a hybrid discrete-continuous mathematical model. In this model, cancer cells described through a particle-spring approach respond to dynamically changing oxygen and DNA damaging drug concentrations described through partial differential equations. We thoroughly explored the behavior of our self-calibrated model under the following common conditions: a fixed layout of the vasculature, an identical initial configuration of cancer cells, the same mechanism of drug action, and one mechanism of cellular response to the drug. We considered one set of simulations in which drug resistance existed prior to the start of treatment, and another set in which drug resistance is acquired in response to treatment. This allows us to compare how both kinds of resistance influence the spatial and temporal dynamics of the developing tumor, and its clonal diversity. We show that both pre-existing and acquired resistance can give rise to three biologically distinct parameter regimes: successful tumor eradication, reduced effectiveness of drug during the course of treatment (resistance), and complete treatment failure

Thermal and Electrical Properties of gamma-NaxCoO2 (0.70 < x < 0.78)

We have performed specific heat and electric resistivity measurements of Na$_{x}$CoO$_{2}$ ($x=0.70$-0.78). Two anomalies have been observed in the specific heat data for $x=0.78$, corresponding to magnetic transitions at $T_{c}=22$ K and $T_{k}\simeq 9$ K reported previously. In the electrical resistivity, a steep decrease at $T_{c}$ and a bending-like variation at $T_{b}$(=120K for $x=0.78$) have been observed. Moreover, we have investigated the $x$-dependence of these parameters in detail. The physical properties of this system are very sensitive to $x$, and the inconsistent results of previous reports can be explained by a small difference in $x$. Furthermore, for a higher $x$ value, a phase separation into Na-rich and Na-poor domains occurs as we previously proposed, while for a lower $x$ value, from characteristic behaviors of the specific heat and the electrical resistivity at the low-temperature region, the system is expected to be in the vicinity of the magnetic instability which virtually exists below $x=0.70$.Comment: 4 pages (3 figures included) and an extra figure (gif), to be published in J. Phys. Soc. Jpn. 73 (9) with possible minor revision