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The interaction of oxygen vacancies and ferroelectric domain walls is of great scientific interest because it leads to different domain-structure behaviors. Here, we use high-resolution scanning transmission electron microscopy to study the ferroelectric domain structure and oxygen-vacancy ordering in a compressively strained Bi 0.9 Ca 0.1 FeO 3-δ thin film. It was found that atomic plates, in which agglomerated oxygen vacancies are ordered, appear without any periodicity between the plates in out-of-plane and in-plane orientation. The oxygen non-stoichiometry with δ ≈ 1 in FeO 2-δ planes is identical in both orientations and shows no preference. Within the plates, the oxygen vacancies form 1D channels in a pseudocubic [010] direction with a high number of vacancies that alternate with oxygen columns with few vacancies. These plates of oxygen vacancies always coincide with charged domain walls in a tail-to-tail configuration. Defects such as ordered oxygen vacancies are thereby known to lead to a pinning effect of the ferroelectric domain walls (causing application-critical aspects, such as fatigue mechanisms and countering of retention failure) and to have a critical influence on the domain-wall conductivity. Thus, intentional oxygen vacancy defect engineering could be useful for the design of multiferroic devices with advanced functionality.

Negatively Charged In-Plane and Out-Of-Plane Domain Walls with Oxygen-Vacancy Agglomerations in a Ca-Doped Bismuth-Ferrite Thin Film