Magnetization and x-ray diffraction have been measured on polycrystalline samples of LaCo0.8−yRh0.2GayO3 for 0≤y≤0.15 in order to understand the spin state of Co3+ through the Ga3+ substitution effect. The ferromagnetic order in LaCo0.8Rh0.2O3 below 15 K is dramatically suppressed by the Ga3+ substitution, where the ferromagnetic volume fraction is linearly decreased. The normal state susceptibility also systematically decreases with the Ga content, from which we find that one Ga3+ ion reduces 4.6 μB per formula unit. We have evaluated how the concentration of the high-spin state Co3+ changes with temperature by using an extended Curie-Weiss law, and have found that the substituted Rh3+ ion stabilizes the high-spin state Co3+ ion down to low temperatures. We find that Ga3+ preferentially replaces the high-spin state Co3+, which makes a remarkable contrast to our previous finding that Rh3+ preferentially replaces the low-spin state Co3+. These results strongly suggest that the magnetically excited state of LaCoO3 at room temperature is a mixed state of high-spin state Co3+ and low-spin state Co3+.
@article{arxiv.1206.4472,
title = {Ga$^{3+}$-substitution effects in the weak ferromagnetic oxide LaCo$_{0.8}$Rh$_{0.2}$O$_{3}$},
author = {Shinichiro Asai and Noriyasu Furuta and Ryuji Okazaki and Yukio Yasui and Ichiro Terasaki},
journal= {arXiv preprint arXiv:1206.4472},
year = {2012}
}