In-Situ Atomic-Scale Observation of Brownmillerite to Ruddlesden–Popper Phase Transition Tuned by Epitaxial Strain in Cobaltites

• Published in: Chinese physics letters 2024-04, Vol.41 (4), p.47701
• Main Authors: Lin, Ting, Gao, Ang, Tang, Zhexin, Lin, Weiguang, Sun, Muhua, Zhang, Qinghua, Wang, Xuefeng, Guo, Er-jia, Gu, Lin
• Format: Article
• Language: English
• ISSN: 0256-307X; 1741-3540
• DOI: 10.1088/0256-307X/41/4/047701

Phase transitions involving oxygen ion extraction within the framework of the crystallographic relevance have been widely exploited for sake of superconductivity, ferromagnetism, and ion conductivity in perovskite-related oxides. However, atomic-scale pathways of phase transitions and ion extraction threshold are inadequately understood. Here we investigate the atomic structure evolution of LaCoO 3 films upon oxygen extraction and subsequent Co migration, focusing on the key role of epitaxial strain. The brownmillerite to Ruddlesden–Popper phase transitions are discovered to stabilize at distinct crystal orientations in compressive- and tensile-strained cobaltites, which could be attributed to in-plane and out-of-plane Ruddlesden–Popper stacking faults, respectively. A two-stage process from exterior to interior phase transition is evidenced in compressive-strained LaCoO 2.5 , while a single-step nucleation process leaving bottom layer unchanged in tensile-strained situation. Strain analyses reveal that the former process is initiated by an expansion in Co layer at boundary, whereas the latter one is associated with an edge dislocation combined with antiphase boundary. These findings provide a chemo-mechanical perspective on the structure regulation of perovskite oxides and enrich insights into strain-dependent phase diagram in epitaxial oxides films.