Ferroelectric Domain Structure in Bi4Ti3O12 Ceramics: Insights from Confocal Raman Microscopy

Bismuth Layer-Structured Ferroelectric (BLSF) materials with Bi4Ti3O12 composition exhibit high ferroelectricity, potential for high-temperature piezoelectricity, and the puzzle of low polarizability, explored via textured ceramics and domain configurations. Here, we show that a distinctive stripe configuration of 90° domains emerges for large platelet-like grains, while the smallest grains, possessing a more equiaxial morphology, exhibit a needle-like domain structure that significantly impacts the ferroelectric properties of the ceramics. The observed hysteresis loops suggest that polarization is effectively clamped, owing to reduced mobility along the needle-like domain walls, thereby leading to a reduction in remnant polarization as grain size diminishes. It is elucidated that the domain structure is intricately linked to both internal stress within the grains and the presence of defects, notably oxygen vacancies, at the domain walls. Consequently, these multifaceted factors are identified as key determinants of the ferroelectric activity within ceramics bearing such a distinctive crystalline structure.