B-site vacancy induced Raman scattering in BaTiO3-based ferroelectric ceramics

Defects, in particular vacancies, play a crucial role in substituted perovskite systems, influencing the structural features that underpin ferroelectricity. B-site vacancies introduce cation disorder in the perovskite lattice and are in fact one of the main driving forces for relaxor behaviour in barium titanate (BaTiO3, BT) based ferroelectrics. In this work, material systems are carefully selected to qualitatively study the change in B-site vacancy concentration for heterovalent substituted BT-based ferroelectric polycrystals. Raman spectroscopy was used to investigate those systems, and B-site vacancy specific Raman modes were identified unambiguously by comparison with charge-compensated BT, where B-site vacancies are absent. This study validates the hypothesis that vacancies induce Raman scattering because of symmetry breaking in the BT lattice, establishing this method as a vital tool to study substitutional defects in ceramic materials.