Complementary study of anisotropic ion conduction in (110)-oriented Ca-doped BiFeO3 films using electrochromism and impedance spectroscopy

Abstract

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 [11¯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.