Enhanced thermoelectric properties of NaxCoO2 whisker crystals

Single-crystalline whiskers of thermoelectric cobalt oxide, NaxCoO2, have been grown by an unconventional method from potassium-containing compositions, and their transport properties, and chemical compositions were determined. The growth mechanism was analyzed and interpreted by means of thermogravimetric analysis. At 300 K, electrical resistivity r and thermoelectric power S of the whisker are 102 u ohm cm and 83 uV/K, respectively. The power-factor, S2/r, thus is enhanced up to ~ 68 uW/K2 cm.Comment: 8 pages, 4 figures, to appear in Appl. Phys. Let

Iron and molybdenum valences in double-perovskite (Sr,Nd)2FeMoO6: electron-doping effect

Double perovskite, (Sr1-xNdx)2FeMoO6, was doped with electrons through partial substitution of divalent Sr by trivalent Nd (0 < x < 0.2). The Fe valence and the degree of B-site order were probed by 57Fe Mossbauer spectroscopy. Replacing Sr by Nd increased the fraction of Fe and Mo atoms occupying wrong sites, i.e. antisite disorder. It had very little effect on the Fe valence: a small but visible increase in the isomer shift was seen for the mixed-valent FeII/III atoms occupying the right site indicating a slight movement towards divalency of these atoms, which was more than counterbalanced by the increase in the fraction of antisite Fe atoms with III valence state. It is therefore argued that the bulk of the electron doping is received by antisite Mo atoms, which - being surrounded by six MoV/VI atoms - prefer the lower IV/V valence state. Thus under Nd substitution, the charge-neutrality requirement inflicts a lattice disorder such that low-valent MoIV/V can exist.Comment: 15 pages, 6 figures, to appear in Solid State Commu

Electrochemical synthesis and properties of CoO2, the x = 0 phase of the AxCoO2 systems (A = Li, Na)

Single-phase bulk samples of the "exotic" CoO2, the x = 0 phase of the AxCoO2 systems (A = Li, Na), were successfully synthesized through electrochemical de-intercalation of Li from pristine LiCoO2 samples. The samples of pure CoO2 were found to be essentially oxygen stoichiometric and possess a hexagonal structure consisting of stacked triangular-lattice CoO2 layers only. The magnetism of CoO2 is featured with a temperature-independent susceptibility of the magnitude of 10-3 emu/mol Oe, being essentially identical to that of a Li-doped phase, Li0.12CoO2. It is most likely that the CoO2 phase is a Pauli-paramagnetic metal with itinerant electrons.Comment: 12 pages, 3 figure

Electronic phase diagram of the layered cobalt oxide system, LixCoO2 (0.0 <= x <= 1.0)

Here we report the magnetic properties of the layered cobalt oxide system, LixCoO2, in the whole range of Li composition, 0 <= x <= 1. Based on dc-magnetic susceptibility data, combined with results of 59Co-NMR/NQR observations, the electronic phase diagram of LixCoO2 has been established. As in the related material NaxCoO2, a magnetic critical point is found to exist between x = 0.35 and 0.40, which separates a Pauli-paramagnetic and a Curie-Weiss metals. In the Pauli-paramagnetic regime (x <= 0.35), the antiferromagnetic spin correlations systematically increase with decreasing x. Nevertheless, CoO2, the x = 0 end member is a non-correlated metal in the whole temperature range studied. In the Curie-Weiss regime (x >= 0.40), on the other hand, various phase transitions are observed. For x = 0.40, a susceptibility hump is seen at 30 K, suggesting the onset of static AF order. A magnetic jump, which is likely to be triggered by charge ordering, is clearly observed at Tt = 175 K in samples with x = 0.50 (= 1/2) and 0.67 (= 2/3), while only a tiny kink appears at T = 210 K in the sample with an intermediate Li composition, x = 0.60. Thus, the phase diagram of the LixCoO2 system is complex, and the electronic properties are sensitively influenced by the Li content (x).Comment: 29 pages, 1 table, 9 figure

Overdoped Cuprates With High Temperature Superconducting Transitions

Evidence for High Tc cuprate superconductivity is found in a region of the phase diagram where non-superconducting Fermi liquid metals are expected. Cu valences estimated independently from both x-ray absorption near-edge structure (XANES) and bond valence sum (BVS) measurements are > 2.3 for structures in the homologous series (Cu0.75Mo0.25)Sr2(Y,Ce)sCu2O5+2s+{\delta} with s = 1, 2, 3, and 4. The s = 1 member, (Cu0.75Mo0.25)Sr2YCu2O7+{\delta}, 0 \leq {\delta} \leq 0.5, is structurally related to YBa2Cu3O7 in which 25% of the basal Cu cations [i.e. those in the chain layer] are replaced by Mo, and the Ba cations are replaced by Sr. After oxidation under high pressure the s = 1 member becomes superconducting with Tc = 88K. The Cu valence is estimated to be ~2.5, well beyond the ~2.3 value for which other High-Tc cuprates are considered to be overdoped Fermi liquids. The increase in valence is attributed to the additional 0.5 oxygen ions added per chain upon oxidation. The record short apical oxygen distance, at odds with current theory, suggests the possibility of a new pairing mechanism but further experiments are urgently needed to obtain more direct evidence. From the structural point of view the members with s \geq 2 are considered to be equivalent to single-layer cuprates. All have Tc ~ 56 K which is significantly higher than expected because they also have higher than expected Cu valences. The XANES-determined valences normalized to give values in the CuO2 layers are 2.24, 2.25, and 2.26 for s = 2, 3, and 4, while the BVS values determined for the valence in the CuO2 layer alone are 2.31-2.34 for the s = 2 and 3 members. No evidence for periodic ordering has been detected by electron diffraction and high resolution imaging studies. The possibility that the charge reservoir layers are able to screen long range coulomb interactions and thus enhance Tc is discussed