Defect structure of oxide ferroelectrics—valence state, site of incorporation, mechanisms of charge compensation and internal bias fields

Abstract

The defect structure of aliovalent transition-metal and rare-earth functional centers in ferroelectric perovskite oxides is characterized by means of multifrequency electron paramagnetic resonance spectroscopy, assisted by density-functional theory calculations. The review is mainly focused on lead zirconate titanate (Pb[Zr x Ti1−x ]O3, PZT) compounds. However, where available also results on ferroelectric ’lead-free’ compounds are discussed. The results include the formation of charged $({\rm Fe}'_{\rm Zr,Ti}-V_{\rm O}^{\bullet \bullet})^{\bullet}$ defect dipoles, causing internal bias fields, multivalence manganese centers, acceptor-type copper functional centers creating isolated oxygen vacancies that promote ionic conductivity, as well as ${\rm Gd}_{\rm Pb}^{\bullet}$ donor-type centers. Moreover, the impact of the defect structure on macroscopic material properties is discussed.