Ionic Tuning of Cobaltites at the Nanoscale

TL;DR

This study demonstrates room-temperature ionic control of oxygen content in (La,Sr)CoO₃ thin films, enabling tunable magnetic, electrical, and structural properties with potential for advanced ionic devices.

Contribution

It introduces a solid-state method to controllably extract oxygen in perovskite films at room temperature, inducing phase separation and structural transformation.

Findings

Oxygen extraction up to 0.5 O/u.c. in 36 nm films.

Continuous variation in Co valence and magnetization.

Formation of oxygen-vacancy ordered brownmillerite phase.

Abstract

Control of materials through custom design of ionic distributions represents a powerful new approach to develop future technologies ranging from spintronic logic and memory devices to energy storage. Perovskites have shown particular promise for ionic devices due to their high ion mobility and sensitivity to chemical stoichiometry. In this work, we demonstrate a solid-state approach to control of ionic distributions in (La,Sr)CoO$_{3}$ thin films. Depositing a Gd capping layer on the perovskite film, oxygen is controllably extracted from the structure, up-to 0.5 O/u.c. throughout the entire 36 nm thickness. Commensurate with the oxygen extraction, the Co valence state and saturation magnetization show a smooth continuous variation. In contrast, magnetoresistance measurements show no-change in the magnetic anisotropy and a rapid increase in the resistivity over the same range of oxygen stoichiometry. These results suggest significant phase separation, with metallic ferromagnetic regions and oxygen-deficient, insulating, non-ferromagnetic regions, forming percolated networks. Indeed, X-ray diffraction identifies oxygen-vacancy ordering, including transformation to a brownmillerite crystal structure. The unexpected transformation to the brownmillerite phase at ambient temperature is further confirmed by high-resolution scanning transmission electron microscopy which shows significant structural - and correspondingly chemical - phase separation. This work demonstrates room-temperature ionic control of magnetism, electrical resistivity, and crystalline structure in a 36 nm thick film, presenting new opportunities for ionic devices that leverage multiple material functionalities.