Subsurface Oxygen Vacancy Mediated Surface Reconstruction and Depolarization of Ferroelectric BaTiO₃ (001) Surface

Abstract The interplay between surface reconstruction and depolarization of ferroelectric oxide surfaces is strongly influenced by oxygen vacancies (V_O). Using in‐situ atomic‐resolution electron microscopy imaging and spectroscopy techniques, it is directly observed that a clean BaTiO₃ (001) surface stabilizes into (2 × 1) BaO‐terminated reconstruction during vacuum annealing. This surface reconstruction is achieved with accommodating BaO deficiency and incorporates TiO_x adunits. The cooperative atomic rumpling in both the surface and subsurface layers, arranged in a tail‐to‐tail configuration, is stabilized by planar accumulation of V_O in the subsurface TiO₂ layer. This reduces the net polarization of surface unit cells, contributing to overall depolarization. Under this atomic rumpling, the polarization‐down (P↓) state is energetically favored over the polarization‐up (P↑) state, as the P↓ state requires less atomic relaxation in the bulk layers to achieve dipole inversion at the subsurface. The energetic preference for V_O in the subsurface TiO₂ layer of the P↓ state is confirmed through calculations of V_O formation energy and the energy barrier for surface‐to‐subsurface migration. These findings reveal that the presence of V_O in the subsurface layer lifts the degeneracy in the double‐well potential between the P↓ and P↑ states in BaTiO₃ (001).