Positive temperature coefficient of the thermal conductivity above room temperature in a perovskite cobaltite

The thermal conductivity above room temperature is investigated for LaCoO₃-based materials showing spin-state and insulator-metal crossovers. A positive temperature coefficient (PTC) of the thermal conductivity is observed during the insulator-metal crossover around 500 K. Our analysis indicates that the phononic thermal transport is also enhanced in addition to the electronic contribution as the insulator-metal crossover takes place. The enhancement of the phononic component is ascribed to the reduction of the incoherent local lattice distortion coupled with the spin/orbital state of each Co³⁺ ion, which is induced by the enhanced spin-state fluctuation between low and excited spin-states. Moreover, fine tunability for the PTC of the thermal conductivity is demonstrated via doping hole-type carriers into LaCoO₃. The observed enhancement ratio of the thermal conductivity κ _T (773 K) / κ _T (323 K) = 2.6 in La_0.95Sr_0.05CoO₃ is the largest value among oxide materials which exhibit a PTC of their thermal conductivity above room temperature. The thermal rectification ratio is estimated to reach 61% for a hypothetical thermal diode consisting of La_0.95Sr_0.05CoO₃ and LaGaO₃, the latter of which is a typical band insulator. These results indicate that utilizing spin-state and orbital degrees of freedom in strongly correlated materials is a useful strategy for tuning thermal transport properties, especially for designing thermal diodes.