Structural and dynamic properties of oxygen vacancies in perovskite oxides—analysis of defect chemistry by modern multi-frequency and pulsed EPR techniques

Multi-frequency and pulsed electron paramagnetic resonance (EPR) provides a sensitive spectroscopic tool to elucidate the defect structure of transition-metal doped perovskite oxides, as well as to monitor dynamic processes of oxygen vacancies in these materials. In this regard, high-frequency EPR spectrometers and pulsed EPR techniques such as the hyperfine sublevel correlation experiment (HYSCORE) may now routinely be used for dedicated investigations, providing considerably more insight than the application of standard continuous-wave EPR. Recent results include the formation of defect complexes between acceptor-type transition-metal centers with either one or two oxygen vacancies for the reason of charge compensation. Furthermore, such defect complexes follow the domain switching upon poling ferroelectric compounds with correspondingly high electric fields. On the other hand, multi-valent manganese functional centers provide trapping centers for electronic and ionic charge carriers (e′, ) such that valency altered acceptor states or defect complexes are formed. Additionally, the trapping of charge carriers at the intrinsic ‘reduced’ B-site ions, and , can be observed by means of EPR spectroscopy.