We have systematically measured the transport properties in the layered rhodium oxide K$_{x}$RhO$_{2}$ single crystals ($0.5lesssim x lesssim 0.67$), which is isostructural to the thermoelectric oxide Na$_{x}$CoO$_{2}$. We find that below $x = 0.64$
the Seebeck coefficient is anomalously enhanced at low temperatures with increasing $x$, while it is proportional to the temperature like a conventional metal above $x=0.65$, suggesting an existence of a critical content $x^{*} simeq 0.65$. For the origin of this anomalous behavior, we discuss a filling-induced Lifshitz transition, which is characterized by a sudden topological change in the cylindrical hole Fermi surfaces at the critical content $x^*$.
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.
We report the thermoelectric transport properties in the orbital-ordered Mott insulating phase of Ca$_2$RuO$_4$ close to and far from equilibrium. Near equilibrium conditions where the temperature gradient is only applied to the sample, an insulating
but non-monotonic temperature variation of the Seebeck coefficient is observed, which is accounted for in terms of a temperature-induced suppression of the orbital order. In non-equilibrium conditions where we have applied high electrical currents, we find that the Seebeck coefficient is anomalously increased in magnitude with increasing external current. The present result clearly demonstrates a non-thermal effect since the heating simply causes a decrease of the Seebeck coefficient, implying a non-trivial non-equilibrium effect such as a modification of the spin and orbital state in currents.
We have examined an isovalent Rh substitution effect on the transport properties of the thermoelectric oxide Ca$_3$Co$_{4}$O$_9$ using single-crystalline form. With increasing Rh content $x$, both the electrical resistivity and the Seebeck coefficien
t change systematically up to $x=0.6$ for Ca$_3$Co$_{4-x}$Rh$_{x}$O$_9$ samples. In the Fermi-liquid regime where the resistivity behaves as $rho=rho_0+AT^2$ around 120 K, the $A$ value decreases with increasing Rh content, indicating that the correlation effect is weakened by Rh $4d$ electrons with extended orbitals. We find that, in contrast to such a weak correlation effect observed in the resistivity of Rh-substituted samples, the low-temperature Seebeck coefficient is increased with increasing Rh content, which is explained with a possible enhancement of a pseudogap associated with the short-range order of spin density wave. In high-temperature range above room temperature, we show that the resistivity is largely suppressed by Rh substitution while the Seebeck coefficient becomes almost temperature-independent, leading to a significant improvement of the power factor in Rh-substituted samples. This result is also discussed in terms of the differences in the orbital size and the associated spin state between Co $3d$ and Rh $4d$ electrons.
We have studied magnetic and transport properties in polycrystalline CaRu1-xScxO3 for 0 =< x =< 0.20 in order to clarify the substitution effects of a non-magnetic trivalent ion. We find that a ferromagnetic transition with Tc = 30 K is observed in S
c-substituted samples. The composition dependence of the Curie-Weiss temperature implies that the magnetic susceptibility has a paramagnetic contribution with negative theta and a ferromagnetic contribution with positive theta. The field dependence of magnetization at 2 K is also understood as a summation of the ferromagnetic and paramagnetic components. These results suggest that CaRu1-xScxO3 is a non-uniform magnetic system. The relationship between the ferromagnetic ordering and the transport properties is also discussed.
We report a novel insulator-insulator transition arising from the internal charge degrees of freedom in the two-dimensional quarter-filled organic salt beta-(meso-DMBEDT-TTF)2PF6. The optical conductivity spectra above Tc = 70 K display a prominent f
eature of the dimer-Mott insulator, characterized by a substantial growth of a dimer peak near 0.6 eV with decreasing temperature. The dimer-peak growth is rapidly quenched as soon as a peak of the charge order shows up below Tc, indicating a competition between the two insulating phases. Our infrared imaging spectroscopy has further revealed a spatially competitive electronic phases far below Tc, suggesting a nature of quantum phase transition driven by material-parameter variations.
Neutron diffraction for a polycrystalline sample of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ and synchrotron x-ray diffraction for polycrystalline samples of LaCo$_{0.9}$Rh$_{0.1}$O$_{3}$ and LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ have been carried out in order to inves
tigate the structural properties related with the spin state of Co$^{3+}$ ions. We have found that the values of the Co(Rh)-O bond lengths in the Co(Rh)O$_{6}$ octahedron of LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$ are nearly identical at 10 K. The lattice volume for the Rh$^{3+}$ substituted samples decreases with the thermal expansion coefficient similar to that of LaCoO$_{3}$ from room temperature, and ceases to decrease around 70 K. These experimental results favor a mixed state consisting of the high-spin-state and low-spin-state Co$^{3+}$ ions, and suggest that the high-spin-state Co$^{3+}$ ions are thermally excited in addition to those pinned by the substituted Rh$^{3+}$ ions.
Dielectric and magnetic properties have been studied for poly-crystalline samples of quasi-one-dimensional frustrated spin-1/2 system Rb$_{2}$(Cu$_{1-x}$M$_{x}$)$_{2}$Mo$_{3}$O$_{12}$(M=Ni and Zn) which does not exhibit a three-dimensional magnetic t
ransition due to quantum spin fluctuation and low dimensionality. A broad peak in the magnetic susceptibility - temperature curves originated from a short range helical ordering at low temperature is suppressed by the Ni and Zn substitution for Cu sites. The capacitance is found to anomalously increase with decreasing T below ~50 K, which is also suppressed by the impurity doping. The behavior of the anomalous capacitance component is found to be strongly connected with that of the magnetic susceptibility for Rb$_{2}$(Cu$_{1-x}$M$_{x}$)$_{2}$Mo$_{3}$O$_{12}$ which indicates that the low-temperature dielectric response is driven by the magnetism.
We examine how the photo-induced carriers contribute the thermoelectric transport, i.e. the nature of the photo-Seebeck effect, in the wide-gap oxide semiconductor ZnO for the first time. We measure the electrical conductivity and the Seebeck coeffic
ient with illuminating light. The light illumination considerably changes the Seebeck coefficient as well as the conductivity, which is sensitive to the photon energy of the illuminated light. By using a simple parallel-circuit model, we evaluate the contributions of the photo-induced carriers to the conductivity and the Seebeck coefficient, whose relationship shows a remarkable resemblance to that in doped semiconductors. Our results also demonstrate that the light illumination increases both the carrier concentration and the mobility, which can be compared with impurity-doping case for ZnO. Future prospects for thermoelectrics using light are discussed.
