Impact of charge transition levels on grain boundary properties in acceptor doped oxide ceramics: A phase-field study

Abstract

Advanced doping strategies enable oxide ceramic functionalities by tailoring bulk defect chemistry and space-charge-layer (SCL) behavior at interfaces. Charge transition levels (CTLs), defined as the Fermi level at which a defect changes its stable charge state, play a central role. Their alignment governs bulk defect chemistry, while their bending within SCLs induces additional charge-state transitions. Incorporating CTLs is therefore essential for a consistent description of defect equilibria and SCL formation. In this work, we propose a defect-chemistry-consistent phase-field model explicitly coupled with CTLs to investigate their role in SCL evolution. The model includes multivalent oxygen vacancies, multivalent acceptor dopants, electrons, and holes. It is applied to Fe-doped SrTiO3 over wide ranges of oxygen partial pressure and temperature, capturing both symmetric SCLs at stationary grain boundaries and asymmetric SCLs during migration. Two distinct grain boundary types, slow and fast boundaries, emerge during migration, consistent with experimental observations. Simulations reveal that CTL-governed bulk defect chemistry, together with CTL-induced charge-state transitions within SCLs, critically determine SCL characteristics. Moreover, CTL-mediated hole transport is significantly faster than acceptor dopant diffusion, modulating solute drag and grain boundary kinetics. Finally, the model predicts grain boundary properties dependent on both thermal history and boundary type, with slow and fast boundaries exhibiting distinct behaviors. This framework links defect chemistry, Fermi level, CTLs, and grain boundary kinetics, providing new insights for designing oxide ceramics with tailored properties.