Tuning of magnetic and electronic states by control of oxygen content in lanthanum strontium cobaltites
We report on the magnetic, resistive, and structural studies of perovskite La$_{1/3}$Sr$_{2/3}$CoO$_{3-δ}$. By using the relation of synthesis temperature and oxygen partial pressure to oxygen stoichiometry obtained from thermogravimetric analysis, we have synthesized a series of samples with precisely controlled $δ=0.00-0.49$. These samples show three structural phases at $δ=0.00-0.15$, $\approx0.25$, $\approx0.5$, and two-phase behavior for other oxygen contents. The stoichiometric material with $δ=0.00$ is a cubic ferromagnetic metal with the Curie temperature $T_{\rm C}=274$ K. The increase of $δ$ to 0.15 is followed by a linear decrease of $T_{\rm C}$ to $\approx$ 160 K and a metal-insulator transition near the boundary of the cubic structure range. Further increase of $δ$ results in formation of a tetragonal $2a_p\times 2a_p \times 4a_p$ phase for $δ\approx 0.25$ and a brownmillerite phase for $δ\approx0.5$. At low temperatures, these are weak ferromagnetic insulators (canted antiferromagnets) with magnetic transitions at $T_{\rm m}\approx230$ and 120 K, respectively. At higher temperatures, the $2a_p\times 2a_p \times 4a_p$ phase is $G$-type antiferromagnetic between 230 K and $\approx$360 K. Low temperature magnetic properties of this system for $δ<1/3$ can be described in terms of a mixture of Co$^{3+}$ ions in the low-spin state and Co$^{4+}$ ions in the intermediate-spin state and a possible spin transition of Co$^{3+}$ to the intermediate-spin state above $T_{\rm C}$. For $δ>1/3$, there appears to be a combination of Co$^{2+}$ and Co$^{3+}$ ions, both in the high-spin state with dominating antiferromagnetic interactions.