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Register a new userSuperconductivity and Cobalt Oxidation State in Metastable Na(x)CoO(2-delta)*yH2O (x ~ 1/3; y ~ 4x)
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We report the synthesis and superconducting properties of a metastable form of the known superconductor NaxCoO2*yH2O (x ~ 1/3, y ~ 4x). Instead of using the conventional bromine-acetonitrile mixture for sodium deintercalation, we use an aqueous bromine solution. Using this method, we oxidize the sample to a point that the sodium cobaltate becomes unstable, leading to formation of other products if not controlled. This compound has the same structure as the reported superconductor, yet it exhibits a systematic variation of the superconducting transition temperature (Tc) as a function of time. Immediately after synthesis, this compound is not a superconductor, even though it contains appropriate amounts of sodium and water. The samples become superconducting with low Tc values after ~ 90 h. Tc continually increases until it reaches a maximum value (4.5 K) after about 260 h. Then Tc drops drastically, becoming non-superconducting approximately 100 h later. Corresponding time-dependent neutron powder diffraction data shows that the changes in superconductivity exhibited by the metastable cobaltate correspond to slow formation of oxygen vacancies in the CoO2 layers. In effect, the formation of these defects continually reduces the cobalt oxidation state causing the sample to evolve through its superconducting life cycle. Thus, the dome-shaped superconducting phase diagram is mapped as a function of cobalt oxidation state using a single sample. The width of this dome based on the formal oxidation state of cobalt is very narrow - approximately 0.1 valence units wide. Interestingly, the maximum Tc in NaxCoO2*yH2O occurs when the cobalt oxidation state is near 3.5. Thus, we speculate that the maximum Tc occurs near the charge ordered insulating state that correlates with the average cobalt oxidation state of 3.5.
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Combining symmetry based considerations with inputs from available experimental results, we make the case that a novel spin-triplet superconductivity triggered by antiferromagnetic fluctuations may be realized in the newly discovered layered cobaltide Na$_x$CoO$_{2}cdot y$H$_2$O. In the proposed picture, unaccessable via resonating-valence-bond physics extrapolated from half-filling, the pairing process is similar to that advanced for Sr$_{2}$RuO$_4$, but enjoys a further advantage coming from the hexagonal structure of the Fermi-surface which gives a stronger pairing tendency.
We have synthesized various samples of the $x=2/3$ phase of sodium cobaltate Na$_{x}$CoO$_{2}$ and performed X-ray powder diffractions spectra to compare the diffraction with the structure proposed previously from NMR/NQR experiments [H. Alloul emph{et al.}, EPL textbf{85}, 47006 (2009)]. Rietveld analysis of the data are found in perfect agreement with those, and confirm the concentration x=2/3 obtained in the synthesis procedure. They even give indications on the atomic displacements of Na inside the unit cell. The detailed NQR data allow us to identify the NQR transitions and electric field gradient (EFG) parameters for 4 cobalt sites and 3 Na sites. The spin-lattice and spin-spin relaxation rates are found much smaller for the non-magnetic Co$^{3+}$ sites than for the magnetic sites on which the holes are delocalized. The atomic ordering of the Na layers is therefore at the source of this ordered distribution of cobalt charges. The method used here to resolve the Na ordering and the subsequent Co charge order can be used valuably for other concentrations of Na.
We have synthesized and characterized four different stable phases of Na ordered Na$_{x}$CoO$_{2}$, for $0.65<x<0.8$. Above 100 K they display similar Curie-Weiss susceptibilities as well as ferromagnetic $q=0$ spin fluctuations in the CoO$_{2}$ planes revealed by $^{23}$Na NMR data. In all phases from $^{59}$Co NMR data we display evidences that the Co disproportionate already above 300 K into non magnetic Co$^{3+}$ and magnetic $approx $Co$^{3.5+}$ sites on which holes delocalize. This allows us to understand that metallic magnetism is favored for these large Na contents. Below 100 K the phases differentiate, and a magnetic order sets in only for $xgtrsim 0.75$ at $T_{N}=$22 K. We suggest that the charge order also governs the low $T$ energy scales and transverse couplings.
We report on a thermal-expansion study of the ferroelectric phase transition in insulating Sr$_{1-x}$Ca$_x$TiO$_3$ ($x=0.009$) and its evolution upon increasing charge-carrier concentration up to $nsimeq 60 times 10^{19}$cm$^{-3}$. Although electric polarization is screened by mobile charge carriers, we find clear signatures of the ferroelectric phase transition in the thermal-expansion coefficient $alpha$ of the weakly doped metallic samples. Upon increasing $n$, the transition temperature $T_mathrm{C}(n)$ and the magnitude of the anomalies in $alpha$ rapidly decrease up to a threshold carrier density $n^star$ above which broadened anomalies remain present. There is no indication for a sign change of $alpha$ as is expected for a pressure-dependent quantum phase transition with $n$ as the control parameter. Thus, the ferroelectriclike transition is either continuously fading away or it transforms to another low-temperature phase above $n^star$, but this change hardly affects the temperature-dependent $alpha(T)$ data.
We probed the local electronic properties of the mixed-valent Co(+4-x) triangular-lattice in Na{x}CoO{2}-yH{2}O by 59-Co NMR. We observed two distinct types of Co sites for x>=1/2, but the valence seems averaged out for x~1/3. Local spin fluctuations exhibit qualitatively the same trend down to ~100 K regardless of the carrier-concentration x, and hence the nature of the electronic ground state. A canonical Fermi-liquid behavior emerges below ~100 K only for x~1/3.
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