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Yoshiaki Kobayashi

Publications and source records attributed to Yoshiaki Kobayashi.

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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.

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Co-NMR Knight Shift of NaxCoO2 \dot yH2O Studied in Both Superconducting Regions of the Tc-nuQ3 Phase Diagram Divided by the Nonsuperconducting Phase

In the temperature (T)-nuQ3 phase diagram of NaxCoO2 \dot yH2O, there exist two superconducting regions of nuQ3 separated by the nonsuperconducting region, where nuQ3 is usually estimated from the peak position of the 59Co-NQR spectra of the 5/2-7/2 transition and well-approximated here as nuQ3~3nuQ,nuQ being the interaction energy between the nuclear quadrupole moment and the electric field gradient. We have carried out measurements of the 59Co-NMR Knight shift (K) for a single crystal in the higher-nuQ3 superconducting phase and found that K begins to decrease with decreasing T at Tc for both magnetic field directions parallel and perpendicular to CoO2-planes. The result indicates together with the previous ones that the superconducting pairs are in the spin-singlet state in both phases, excluding the possibility of the spin-triplet superconductivity in this phase diagram. The superconductivity of this system spreads over the wide nuQ3 regions, but is suppressed in the narrow region located at the middle point of the region possibly due to charge instability.

cond-mat.supr-con↗

Ferroelectric Transition Induced by the Incommensurate Magnetic Ordering in LiCuVO4

A ferroelectric transition occurring simultaneously with helical spin order has been found in both the polycrystalline and single crystal samples of LiCuVO4. The system has Cu2+ spins (s=1/2) of the CuO2 chains formed of edge-sharing CuO4 squares. Possibly due to the frustrated nature caused by the competition between the nearest-neighbor and next-nearest-neighbor exchange interactions, Cu spins exhibit, as has been already reported, the helical magnetic order with the incommensurate modulation vector Q along the chain direction and with the helical axis e3 perpendicular to the CuO4 squares. The electric polarization P can be understood by the recently predicted relation (P is proportional to Q*e3). The transition temperature has been found to be gradually suppressed by the applied magnetic field.

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Existence of the Co3+ Low Spin State in TbBaCo2O5.5

NMR studies have been carried out on a single crystal sample of TbBaCo2O5.5 with the oxygen-deficient perovskite structure. We have also carried out neutron diffraction studies and added new results to our previously published data. By analyzing these data, the magnetic structures and the spin states of the system, which have been the subjects of strong controversies, are argued in the ferromagnetic and antiferromagnetic phases. We show that among various magnetic structures ever proposed, only our non-collinear ones can reproduce all experimental results accumulated up to now.

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Magnetic properties of superconducting cobalt oxides NaxCoO2.yH2O

Studies of the NMR Knight shift K of Na0.3CoO2.yH2O have been carried out in detail. The suppression of K by the occurrence of the superconductivity reported previously by the present authors in both magnetic field directions perpendicular and parallel to the c axis has been confirmed, indicating that the Cooper pairs are in the singlet state. The anisotropy of the suppression amplitudes is consistent with the anisotropy of the hyperfine coupling constant Aspin estimated by the K-kai plot. It has also been found that even samples, which do not exhibit a significant amount of the Curie-Weiss-like increase of the uniform magnetic susceptibility kai with decreasing temperature T, exhibit the superconducting transition, which indicates that the superconducting Na0.3CoO2.1.3H2O is not necessarily be in the proximity region of the ferromagnetic phase. It has also been confirmed that the superconducting transition temperature Tc of the samples prepared by mixing Na0.7CoO2, H2O (or D2O) and bromine for 4 h, and separating the resultant powder from the solution by filtration, depends on the elapsed time t after filtration. For these samples, the Curie constant of kai estimated at low temperatures increases with t, supporting the idea that the number of the lattice imperfection possibly due to the oxygen-vacancy-formation increases with t. Even for such samples, the superconductivity appears, which seems to exclude the possibility of the anisotropic superconducting order parameter. These results are favorable for the full-gapped superconductivity.

cond-mat.supr-con↗

Search for Magnetic Excitation Spectra of NaxCoO2.yD2O -Neutron Scattering-

Neutron inelastic scattering studies on aligned crystals of NaxCoO2.yD2O have been carried out. Significant scattering has been observed for phonons originating from the vibrations of the short-range ordered D2O molecules. No firm evidence for the magnetic fluctuations has been found for the NaxCoO2.yD2O, while the very weak intensity modulation observed in the j scans along (1/2, 1/2, j) suggests the existence of the antiferromagnetic fluctuations in the non-deuterated parts of the sample, the volume fraction of which is estimated to be about 26 %. The present results indicate that magnetic fluctuations, especially ferromagnetic ones are rather weak, in the deuterated system, which is consistent with the results of the NMR Knight shift reported by the present authors' group. We discuss the short-range ordered state of D2O, too by analyzing the observed diffuse scattering.

cond-mat.supr-con↗

Magnetic Correlation of NaxCoO2 and Successive Phase Transitions of Na0.5CoO2 -NMR and Neutron Diffraction Studies-

Data taken by various kinds of methods including NMR/NQR and neutron scattering are presented for NaxCoO2, in particular, for Na0.5CoO2. Attentions have also been paid to the x dependence of the electronic nature. The pseudo-gap-like behavior observed in the region of x<xc~0.6 is emphasized. For samples with x<0.6, signals from two kinds of Co sites with different quadrupole frequencies nQ, ~4.1 MHz and ~2.8 MHz were observed, and the former value of nQ, which is nearly equal to that of the superconducting system Na0.3CoO2.yH2O, becomes dominant with decreasing x to 0.3. For Na0.5CoO2, the Co sites with the larger nQ value have the larger magnetic moments. They align antiferromagnetically at Tc1~87 K with their direction within the plane, while the Co sites with the smaller nQ value have the smaller moments. They align along the direction parallel to the c axis. The ordered moments at the two distinct sites exhibit the same T dependences, indicating that the existence of these sites is not due to a macroscopic phase separation. Although we have observed the splitting of the zero-field NMR signals from the Co sites with the smaller nQ value at the second transition temperature Tc2~53 K, any other anomaly of the ordered magnetization has not been observed there in the T dependences of the neutron and the NMR data. As x decreases, the two-dimensional nature of the electrons is enhanced and the antiferromagnetic correlation increases. Based on these results, the superconducting pair state in Na0.3CoO2.yH2O is discussed.

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59Co-NMR Knight Shift of Aligned Crystals and Polycrystalline Samples of Superconducting Na0.3CoO2.1.3H2O

Temperature (T) dependence of 59Co-NMR Knight shifts K of Na0.3CoO2.1.3H2O has been studied, where samples of randomly oriented powder and aligned crystals have been used for the applied magnetic fields H // ab plane and H //c-axis, respectively. For both directions of H, the shift K decreases below the superconducting transition temperature Tc(H) with decreasing T, indicating that the superconducting electron pairs are in the singlet state. The upper critical fields Hc2(T) determined from the K(H)-T curves are found to be consistent with the values reported by the resistivity measurements for both directions of H.

cond-mat.supr-con↗

Transport and Magnetic Studies on the Spin State Transition of Pr1-xCaxCoO3 up to High Pressure

Transport and magnetic measurements and structural and NMR studies have been carried out on (Pr1-yR'y)1-xAxCoO3 {R'=(rare earth elements and Y); A=(Ca, Ba and Sr)} at ambient pressure or under high pressure. The system exhibits a phase transition from a nearly metallic to an insulating state with decreasing temperature T, where the low spin (LS) state of Co3+ is suddenly stabilized. For y=0, we have constructed a T-x phase diagram at various values of the external pressure p. It shows that the (T, x) region of the low temperature phase, which is confined to a very narrow region around x=0.5 at ambient pressure, expands as p increases, suggesting that the transition is not due to an order-disorder type one. For the occurrence of the transition, both the Pr and Ca atoms seem to be necessary. The intimate relationship between the local structure around the Co ions and the electronic (or spin) state of Co3+ ions is discussed: For the smaller unit cell volume or the smaller volume of the CoO6 octahedra and for the larger tilting angle of the octahedra, the temperature of the transition becomes higher. The role of the carriers introduced by the doping of the A atoms, is also discussed. By analyzing the data of 59Co-NMR spectra and magnetic susceptibilities of Pr1-xCaxCoO3 the energy separations among the different spin states of Co3+ and Co4+ are roughly estimated.

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Ru-NMR Studies and Specific Heat Measurements of Bi3Ru3O11 and La4Ru6O19

Specific heats measurements and Ru-NMR studies have been carried out for Bi3Ru3O11 and La4Ru6O19, which commonly have three-dimensional linkages of edge-sharing pairs of RuO6 octahedra. The Knight shifts, the nuclear spin-lattice relaxation rates 1/T1 and the electronic specific heats Cel of these systems exhibit anomalous temperature (T) dependence at low temperatures, as was pointed out by Khalifah et al. [Nature 411 (2001) 660.] for the latter system based on their experimental data of the resistivity, magnetic susceptibility and electronic specific heat. Ratios of 1/T1T to the square of the spin component of the isotropic Knight shift, Kspin estimated for these systems at low temperatures suggest that they have antiferromagnetic (AF) spin fluctuations. It is confirmed by the fact that the T-dependences of 1/T1T and Cel/T of the present systems can be explained by the self-consistent renormalization theory for three dimensional itinerant electron systems with AF spin fluctuations. All these results suggest that the AF fluctuations are the primary origin of the characteristics of their low temperature physical behavior.

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59Co-NQR study on superconducting NaxCoO2.yH2O

Layered Co oxide NaxCoO2.yH2O with a superconducting transition temperature Tc =4.5 K has been studied by 59Co NQR. The nuclear spin relaxation rate 1/59T1 is nearly proportional to temperature T in the normal state. In the superconducting state, it exhibits the coherence peak and decreases with decreasing T below ~0.8Tc. Detailed comparison of the 1/T1T values and the magnetic susceptibilities between NaxCoO2.yH2O and NaxCoO2 implies that the metallic state of the former system is closer to a ferromagnetic phase than that of the latter. These experimental results impose a restriction on the mechanism of the superconductivity.

cond-mat.supr-con↗

59Co-NMR Knight Shift of the Superconducting NaxCoO2.yH2O

Layered Co oxide NaxCoO2.yH2O with the superconducting transition temperature Tc =4.5 K has been studied by 59Co-NMR. The Knight shift K estimated from the observed spectra for powder sample exhibits almost temperature(T)-independent behavior above Tc and decreases with decreasing T below Tc. This result and the existence of the coherence peak in the spin-lattice-relaxation-rate versus T curve reported by the present authors indicate, naively speaking, that the singlet order parameter with s-wave symmetry is realized in NaxCoO2.yH2O. Differences of the observed behaviors between the spectra of the non-aligned sample and the one aligned in epoxy adhesive by applying the external magnetic field are discussed.

cond-mat.supr-con↗

Spin-Glass-like Transition and Hall Resistivity of Y2-xBixIr2O7

Various physical properties of the pyrochlore oxide Y2-xBixIr2O7 have been studied. The magnetizations M measured under the conditions of the zero-field-cooling(ZFC) and the field-cooling(FC) have different values below the temperature T=TG. The anomalous T-dependence of the electrical resistivities r and the thermoelectric powers S observed at around TG indicates that the behavior of the magnetization is due to the transition to the state with the spin freezing. In this spin-frozen state, the Hall resistivities rH measured with the ZFC and FC conditions are found to have different values, too, in the low temperature phase (T<TG). Possible mechanisms which induce such the hysteretic behavior are discussed.

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Transport and Magnetic Properties of R1-xAxCoO3 (R=La, Pr and Nd; A=Ba, Sr and Ca)

Transport and magnetic measurements have been carried out on perovskite Co-oxides R1-xAxCoO3 (R=La, Pr, and Nd; A=Ba, Sr and Ca; 0<x<0.5: All sets of the R and A species except Nd1-xBaxCoO3 have been studied.). With increasing the Sr- or Ba-concentration x, the system becomes metallic ferromagnet with rather large magnetic moments. For R=Pr and Nd and A=Ca, the system approaches the metal- insulator phase boundary but does not become metallic. The magnetic moments of the Ca-doped systems measured with the magnetic field H=0.1 T are much smaller than those of the Ba- and Sr-doped systems. The thermoelectric powers of the Ba- and Sr-doped systems decrease from large positive values of lightly doped samples to negative ones with increasing doping level, while those of Ca-doped systems remain positive. These results can be understood by considering the relationship between the average ionic radius of R1-xAx and the energy difference between the low spin and intermediate spin states. We have found the resistivity-anomaly in the measurements of Pr1-xCaxCoO3 under pressure in the wide region of x, which indicates the existence of a phase transition different from the one reported in the very restricted region of x~0.5 at ambient pressure [Tsubouchi et al. Phys. Rev. B 66 (2002) 052418.]. No indication of this kind of transition has been observed in other species of R.

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Transport and NQR Studies of Nd1.6-xCexSr0.4CuO4 with T* Structure

Transport and Cu-NQR studies have been carried out for the T*-type high temperature superconducting Cu oxide Nd1.6-xCexSr0.4CuO4 with single layered CuO2 planes formed by CuO5 pyramids. No anomaly related to the static or quasi static "stripe" order has been observed in the temperature T and x dependence of the thermoelectric powers S. We have not found such kind of anomaly in the x dependence of the superconducting transition temperature Tc, either. Although the decrease of the Cu NQR intensity with decreasing T (wipeout) has been observed in this system, it can be understood by considering the loss of the itinerant nature of the electrons, which takes place in the proximity region of the metal-insulator phase boundary, and cannot be connected with the static or quasi static "stripe" order.

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