We report giant thermopower S = 2.5 mV/K in CoSbS single crystals, a material that shows strong high-temperature thermoelectric performance when doped with Ni or Se. Changes of low temperature thermopower induced by magnetic field point to mechanism of electronic diffusion of carriers in the heavy valence band. Intrinsic magnetic susceptibility is consistent with the Kondo- Insulator-like accumulation of electronic states around the gap edges. This suggests that giant thermopower stems from temperature-dependent renormalization of the non-interacting bands and buildup of the electronic correlations on cooling.
High-temperature thermopower is interpreted as entropy that a carrier carries. Owing to spin and orbital degrees of freedom, a transition metal perovskite exhibits large thermopower at high temperatures. In this paper, we revisit the high-temperature thermopower in the perovskites to shed light on the degrees of freedom. Thus, we theoretically derive an expression of thermopower in one-dimensional octahedral-MX6-clusters chain using linear-response theory and electronic structure calculation of the chain based on the tight-binding approximation. The derived expression of the thermopower is consistent with the extended Heikes formula and well reproduced experimental data of several perovskite oxides at high temperatures. In this expression, a degeneracy of many electron states in octahedral ligand field (which is characterized by multiplet term) appears instead of the spin and orbital degeneracies. Complementarity in between our expression and the extended Heikes formula is discussed.
The nature of the low temperature ground state of the pyrochlore compound Tb2Ti2O7 remains a puzzling issue. Dynamic fluctuations and short-range correlations persist down to 50 mK, as evidenced by microscopic probes. In parallel, magnetization measurements show irreversibilities and glassy behavior below 200 mK. We have performed magnetization and AC susceptibility measurements on four single crystals down to 57 mK. We did not observe a clear plateau in the magnetization as a function of field along the [111] direction, as suggested by the quantum spin ice model. In addition to a freezing around 200 mK, slow dynamics are observed in the AC susceptibility up to 4 K. The overall frequency dependence cannot be described by a canonical spin-glass behavior.
We prove the direct link between low temperature magnetism and high temperature sodium ordering in NaxCoO2 using the example of a heretofore unreported magnetic transition at 8 K which involves a weak ferromagnetic moment. The 8 K feature is characterized in detail and its dependence on a diffusive sodium rearrangement around 200 K is demonstrated. Applying muons as local probes this process is shown to result in a reversible phase separation into distinct magnetic phases that can be controlled by specific cooling protocols. Thus the impact of ordered sodium Coulomb potential on the CoO2 physics is evidenced opening new ways to experimentally revisit the NaxCoO2 phase diagram.
The increasing worldwide energy consumption calls for the design of more efficient energy systems. Thermoelectrics could be used to convert waste heat back to useful electric energy if only more efficient materials were available. The ideal thermoelectric material combines high electrical conductivity and thermopower with low thermal conductivity. In this regard, the intermetallic type-I clathrates show promise with their exceedingly low lattice thermal conductivities [1]. Here we report the successful incorporation of cerium as guest atom into the clathrate crystal structure. In many simpler intermetallic compounds, this rare earth element is known to lead, via the Kondo interaction, to strong correlation phenomena including the ocurrence of giant thermopowers at low temperatures [2]. Indeed, we observe a 50% enhancement of the thermopower compared to a rare earth-free reference material. Importantly, this enhancement occurs at high temperatures and we suggest that a `rattling enhanced Kondo interaction [3] underlies this effect.
We investigated the effect of pressure on the magnetic and thermoelectric properties of Sr$_{3.1}$Y$_{0.9}$Co$_{4}$O$_{10+delta }$. The magnetization is reduced with the application of pressure, reflecting the spin-state modification of the Co$^{3+}$ ions into the nonmagnetic low-spin state. Accordingly, with increasing pressure, the Seebeck coefficient is enhanced, especially at low temperatures, at which the effect of pressure on the spin state becomes significant. These results indicate that the spin-orbital entropy is a key valuable for the thermoelectric properties of the strongly correlated cobalt oxides.