Interactions between Mn dopant and oxygen vacancy for insulation performance of BaTiO3

We performed first-principles calculations and electron spin resonance (ESR) measurements on Mn-doped perovskite BaTiO3 (BT) ceramics in order to investigate the interactions between Mn dopant and O vacancy (VO). We discovered the following two. First, VOs are stabilized at the nearest neighbor O site of Mn at a Ti site and this results in the suppression of VO diffusion. Second, electrons generated by the formation of VOs are trapped in unoccupied Mn-3d orbitals in the BT bandgap. This indicates that the valence state of Mn changes according to the VO density. We synthesized Mn-doped BT by varying the partial pressure of O2 gas and examined the Mn valence states with ESR measurements. We successfully observed that the majority type of Mn ions (2+, 3+, and 4+) depends on O2 gas pressure of the firing atmosphere. According to these theoretical and experimental investigations, we concluded that Mn dopants have two effects, i.e., VO and electron carrier trapping. Moreover, the mechanisms of Mn doping in BT i...