Near-room temperature ferromagnetic insulating state in highly distorted LaCoO<sub>2.5</sub> with CoO<sub>5</sub> square pyramids.

Zhang, Qinghua; Gao, Ang; Meng, Fanqi; Jin, Qiao; Lin, Shan; Wang, Xuefeng; Xiao, Dongdong; Wang, Can et al. · Nat Commun · 2021

basic_science · Level V

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Abstract

Dedicated control of oxygen vacancies is an important route to functionalizing complex oxide films. It is well-known that tensile strain significantly lowers the oxygen vacancy formation energy, whereas compressive strain plays a minor role. Thus, atomic reconstruction by extracting oxygen from a compressive-strained film is challenging. Here we report an unexpected LaCoO<sub>2.5</sub> phase with a zigzag-like oxygen vacancy ordering through annealing a compressive-strained LaCoO<sub>3</sub> in vacuum. The synergetic tilt and distortion of CoO<sub>5</sub> square pyramids with large La and Co shifts are quantified using scanning transmission electron microscopy. The large in-plane expansion of CoO<sub>5</sub> square pyramids weaken the crystal field splitting and facilitated the ordered high-spin state of Co<sup>2+</sup>, which produces an insulating ferromagnetic state with a Curie temperature of ~284 K and a saturation magnetization of ~0.25 μ<sub>B</sub>/Co. These results demonstrate that extracting targeted oxygen from a compressive-strained oxide provides an opportunity for creating unexpected crystal structures and novel functionalities.