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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 (Bi1-xCaxFeO3-δ) films. Our demonstration relies on the finding that a compositional phase transition occurs by varying Ca doping ratio across xCa ≃ 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. Phase transition points can be used to reduce the ionic migration activation energy. Here, the authors find a lowered activation energy associated with oxygen transport at a compositional phase transition point in Ca-doped bismuth ferrite films. [ABSTRACT FROM AUTHOR]

Oxygen vacancies are ubiquitous in oxides, and taking advantage of their mobility is the cornerstone for a variety of future applications. The visualization and quantification of collective defect flow based on electrochromism is a powerful approach to explore oxygen kinetics and electrochemical reaction even in cases that electronic conduction is considerably mixed, but whether or not the measured kinetic properties harmonize with those obtained by the conventional impedance spectroscopy remains veiled. Here, we identify complementary relationships between the two methods by investigating the oxygen vacancy transport in Ca 30%-doped bismuth ferrite thin films epitaxially grown on SrTiO3 (110) substrates. We find that the activation energy of ionic hopping is 0.78 (or 0.92 eV) for the application of an electric bias along [001] (or [1 1 ¯ 0]) due to the grain elongation along [001]. We anneal the films in an N2 gas environment at high temperatures to suppress the electronic contribution for access to standard impedance spectroscopy. The oxygen kinetic properties obtained from the two methods are consistent with each other, complementarily revealing the collective phase evolution as well as the ionic impedance of the bulk, grain boundary, and interfacial regions. These comparative works provide useful insights into ionic defect conduction in oxides in an intuitive and quantitative manner. [ABSTRACT FROM AUTHOR]