Critical ionic transport across an oxygen-vacancy ordering transition.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 36050294.
- Also identified by DOI 10.1038/s41467-022-32826-8 and PMC identifier 9437025.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Phase transition points can be used to critically reduce the ionic migration activation energy, which is important for realizing high-performance electrolytes at low temperatures. Here, we demonstrate a route toward low-temperature thermionic conduction in solids, by exploiting the critically lowered activation energy associated with oxygen transport in Ca-substituted bismuth ferrite (Bi<sub>1-x</sub>Ca<sub>x</sub>FeO<sub>3-δ</sub>) films. Our demonstration relies on the finding that a compositional phase transition occurs by varying Ca doping ratio across x<sub>Ca</sub> ≃ 0.45 between two structural phases with oxygen-vacancy channel ordering along <100> or <110> crystal axis, respectively. Regardless of the atomic-scale irregularity in defect distribution at the doping ratio, the activation energy is largely suppressed to 0.43 eV, compared with ~0.9 eV measured in otherwise rigid phases. From first-principles calculations, we propose that the effective short-range attraction between two positively charged oxygen vacancies sharing lattice deformation not only forms the defect orders but also suppresses the activation energy through concerted hopping.