Phase evolution of layered cobalt oxides versus varying corrugation of the cobalt-oxygen basal plane

TL;DR

This study uses density functional calculations to explore how the phase evolution of layered cobalt oxides depends on the corrugation of the cobalt-oxygen basal plane, revealing a transition from antiferromagnetic insulator to a mixed magnetic state.

Contribution

The paper introduces a spin-state model linking plane corrugation to magnetic and electronic phase transitions in layered cobalt oxides, supported by density functional calculations.

Findings

Decreased corrugation leads to a transition from HS AFM insulator to a mixed AFM/FM system.

Delocalized pdσ holes are crucial for insulator-metal and magnetic transitions.

Varying ionic size of neighboring layers can control phase states in LCOs.

Abstract

A general spin-state model and a qualitative physical picture have been proposed for a class of lately synthesized layered cobalt oxides (LCOs) by means of density functional calculations. As the plane corrugation of the cobalt-oxygen layer decreases, the LCOs evolve from a high-spin (HS) superexchange-coupled antiferromagnetic (AFM) insulator to an almost-HS AFM/ferromagnetic (FM) competing system where the FM coupling is mediated via the p-d exchange by an increasing amount of delocalized pd\sigma holes having mainly the planar O 2p character. It is tentatively suggested that the delocalized holes more than 0.3 per CoO_{2} basal square are likely necessary for the insulator-metal and/or AFM-FM transitions in the corrugation-weakened LCOs. A phase control may be realized in LCOs by varying the plane corrugation (thus modifying the hole concentration) through an ionic-size change of the neighboring layers on both sides of the cobalt-oxygen layer. In addition, a few experiments are suggested for a check of the present model and picture.