Computer modelling of point defects in ABO₃ perovskites and MgO

We present results for basic intrinsic defects: F-type electron centers (O vacancy which trapped one or two electrons) and hole polarons bound to Mg or K vacancy in ionic MgO and partly covalent KNbO₃ perovskite, respectively. We demonstrate that a considerable covalency of the perovskite chemical bonding makes the F-type centers therein much more similar to defects in partly-covalent quartz-type oxides rather than the conventional F centers in alkali halides and ionic MgO. Both one-site (atomic) and two-site (molecular) polarons are expected to coexist in KNbO₃ characterized by close absorption energies. Our calculations confirm existence of the self-trapped electron polarons in KNbO₃, KTaO₃, BaTiO₃, and PbTiO₃ crystals. The self-trapped electron is mostly localized on B-type ion due to a combination of breathing and Jahn-Teller modes of nearest six oxygen ion displacements. The relevant lattice relaxation energies are typically 0.2-0.3 eV, whereas the optical absorption energies 0.7-0.8 eV, respectively. According to our calculations, the absorption energy of a bound electron polaron in KNbO₃ by 0.1 eV exceeds that for the self-trapped electron polaron and equals 0.88 eV.