Tuning of magnetic and electronic states by control of oxygen content in lanthanum strontium cobaltites

TL;DR

This study investigates how varying oxygen content in lanthanum strontium cobaltites affects their magnetic, electronic, and structural properties, revealing phase transitions and magnetic behaviors linked to different cobalt oxidation and spin states.

Contribution

It provides a detailed correlation between oxygen stoichiometry and the structural, magnetic, and electronic phases in La$_{1/3}$Sr$_{2/3}$CoO$_{3- ext{δ}}$, including synthesis control and phase characterization.

Findings

Controlled oxygen content induces structural phase transitions.

Magnetic properties vary with oxygen stoichiometry, showing ferromagnetic, antiferromagnetic, and insulating behaviors.

Identification of spin states of cobalt ions across different phases.

Abstract

We report on the magnetic, resistive, and structural studies of perovskite La$_{1/3}$Sr$_{2/3}$CoO$_{3-\delta}$. 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 $\delta=0.00-0.49$. These samples show three structural phases at $\delta=0.00-0.15$, $\approx0.25$, $\approx0.5$, and two-phase behavior for other oxygen contents. The stoichiometric material with $\delta=0.00$ is a cubic ferromagnetic metal with the Curie temperature $T_{\rm C}=274$ K. The increase of $\delta$ 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 $\delta$ results in formation of a tetragonal $2a_p\times 2a_p \times 4a_p$ phase for $\delta\approx 0.25$ and a brownmillerite phase for $\delta\approx0.5$. 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 $\delta<1/3$ 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 $\delta>1/3$, there appears to be a combination of Co$^{2+}$ and Co$^{3+}$ ions, both in the high-spin state with dominating antiferromagnetic interactions.