Local structural disorder and its influence on the average global structure and polar properties in Na0.5Bi0.5TiO3

Abstract

Na${}_{0.5}$Bi${}_{0.5}$TiO${}_{3}$ (NBT) and its derivatives have prompted a great surge in interest owing to their potential as lead-free piezoelectrics. In spite of five decades since its discovery, there is still a lack of clarity on crucial issues such as the origin of significant dielectric relaxation at room temperature, structural factors influencing its depoling, and the status of the recently proposed monoclinic ($Cc$) structure vis-\`a-vis the nanosized structural heterogeneities. In this work, these issues are resolved by comparative analysis of local and global structures on poled and unpoled NBT specimens using electron, x-ray, and neutron diffraction in conjunction with first-principles calculation, dielectric, ferroelectric, and piezoelectric measurements. The reported global monoclinic ($Cc$) distortion is shown not to correspond to the thermodynamic equilibrium state at room temperature. The global monocliniclike appearance rather owes its origin to the presence of local structural and strain heterogeneities. Poling removes the structural inhomogeneities and establishes a long-range rhombohedral distortion. In the process the system gets irreversibly transformed from a nonergodic relaxor to a normal ferroelectric state. The thermal depoling is shown to be associated with the onset of incompatible in-phase tilted octahedral regions in the field-stabilized long range rhombohedral distortion.