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Register a new user59Co, 23Na, and 1H NMR Studies of Double-Layer Hydrated Superconductors NaxCoO2-yH2O
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We present our NMR studies of double-layer hydrated cobalt oxides NaxCoO2-yH2O (x ~ 0.35, y ~ 1.3) with various Tc = 0 - 4.8 K and magnetic transition temperatures. High-resolution $^{1}$H NMR spectrum served as an evidence for the existence of H$_{3}$O$^{+}$ oxonium ions. $^{23}$Na nuclear spin-lattice relaxation rates served to detect local field fluctuations sensitive to Tc. $^{59}$Co nuclear quadrupole resonance (NQR) spectra served to classify the various Tc samples. From the classification by $^{59}$Co NQR frequency, the double-layer hydrated compounds were found to have two superconducting phases closely located to a magnetic phase. In the normal state and at a magnetic field in the $ab$-plane, two $^{59}$Co NMR signals with different Knight shifts and different $^{59}$Co nuclear spin-lattice relaxation times $^{59}T_{1}$ were observed. The two $^{59}$Co NMR signals suggest magnetic disproportionation of two Co sites or in-plane (XY) anisotropy of a single Co site. Non Korringa behavior and power law behavior in zero-field NQR 1/$^{59}T_{1}$ above and below Tc suggest non-Fermi liquid and unconventional superconductivity.
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The Raman spectra of the parent compound NaxCoO2 (x=0.75) and the superconducting oxyhydrates NaxCoO2.yH2O with different superconducting temperatures (Tc) have been measured. Five Raman active phonons around 195 cm-1 (E1g), 482 cm-1, 522 cm-1, 616 cm-1 (3E2g), 663 cm-1 (A1g) appear in all spectra. These spectra change systematically along with the intercalation of H2O and superconducting properties. In particular, the Raman active phonons (A1g and E1g) involving the oxygen motions within the Co-O layers show up monotonous decrease in frequency along with superconducting temperature Tc. The fundamental properties and alternations of other active Raman phonons in the superconducting materials have also been discussed.
We synthesized Nax(H3O)zCoO2yH2O samples with various Na/H3O ratios but with the constant Co valence of s = +3.40, and measured their magnetic properties to draw phase diagrams of the system. The superconductivity is very sensitive to the Na/H3O ratio. With varying x under fixed s of +3.40, magnetically ordered phase appears in the intermediate range of x sandwiched by two separated superconducting phases, suggesting that the superconductivity is induced by moderately strong magnetic interactions. In the vicinity of the magnetic phase, transition from the superconducting state to the magnetically ordered state was induced by applying high magnetic field. This transition is of the second order, at least, above 1.8 K. The upper-critical field is expected to be much higher than the Pauli limit for a phase located far away from the magnetic phase regarding the Na/H3O ratio.
Various samples of sodium cobalt oxyhydrate with relatively large amounts of Na$^{+}$ ions were synthesized by a modified soft-chemical process in which a NaOH aqueous solution was added in the final step of the procedure. From these samples, a superconducting phase diagram was determined for a section of a cobalt valence of $sim$+3.48, which was compared with a previously obtained one of $sim$+3.40. The superconductivity was significantly affected by the isovalent exchanger of Na$^{+}$ and H$_{3}$O$^{+}$, rather than by variation of Co valence, suggesting the presence of multiple kinds of Fermi surface. Furthermore, the high-field magnetic susceptibility measurements for one sample up to 30 T indicated an upper critical field much higher than the Pauli limit supporting the validity of the spin-triplet pairing mechanism.
Here we present results of accurate wet-chemical redox analyses, revealing that the oxidation number of cobalt in the newly discovered CoO2-layer superconductor, NaxCoO2 yH2O (x ~ 0.36, y ~ 1.3) is ~ 3.46. This value is significantly lower than the one (~ 3.64) expected on the basis of the value determined for the Na to Co stoichiometry ratio, x. The lower-than-expected value for the Co oxidation state may be alternatively explained by presence of oxygen vacancies or excess protons. Moreover, the result implies that rather than an electron-doped Co(IV) lattice the phase should be considered as a hole-doped Co(III) lattice.
$^{59}$Co NMR spectra in oriented powders of Na$_{0.35}$CoO$_{2}$ and in its hydrated superconducting phase (HSC) Na$_{0.35}$CoO$_{2}$,1.3H$_{2}$O reveal a single electronic Co state with identical $T$ independent NMR shift tensor. These phases differ markedly from Na$_{0.7}$CoO$_{2}$, in which we resolve 3 types of Co sites. The large T variation of their spin susceptibilities $chi ^{s}$ and the anisotropy of the orbital susceptibility $chi ^{orb}$ allow us to conclude that charge disproportionation occurs, in a non magnetic Co$^{3+}$ and two magnetic sites with about 0.3 and 0.7 holes in the $t_{2g}$ multiplet. The data are consistent with those for the single Co site in the anhydrous and HSC phase assuming the expected Co$^{3.65+}$ charge.
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