Impurity-Induced Spin-State Crossover in La0.8Sr0.2Co1−xAlxO3

We have prepared a set of polycrystalline samples of La 0.8 Sr 0.2 Co 1 − x Al x O 3 ( 0 ≤ x ≤ 0.2 ), and have measured the magnetization as functions of temperature and magnetic field. We find that the average spin number per Co ion ( S Co ) evaluated from the room-temperature susceptibility is around 1.2–1.3 and independent of x. However, we further find that S Co evaluated from the saturation magnetization at 2 K is around 0.3–0.7, and decreases dramatically with x. This naturally indicates that a significant fraction of the Co 3 + ions experience a spin-state crossover from the intermediate- to low-spin state with decreasing temperature in the Al-substituted samples. This spin-state crossover also explains the resistivity and the thermopower consistently. In particular, we find that the thermopower is anomalously enhanced by the Al substitution, which can be consistently explained in terms of an extended Heikes formula.

Thermoelectric Power in Ruthenates : Dominant Role of the Spin Degeneracy Term

The Seebeck coefficients of several ruthenates which structures derive from the perovskite, have been measured up to 800K. All the values above 300K are found to be in the range +25μV.K-1 to +35 μV.K-1, with a very weak dependence on both T absolute value and electrical resistivity. This demonstrates that S at high T depends mainly on the spin degeneracy term of the modified Heikes formula. The insensitivity of thermopower to the chemical doping confirms the applicability of the model. The present study also shows the good properties of ruthenates as thermoelectric p-type oxides for high T energy conversion.