Electronic and Structural Transitions of LaAlO(3)/SrTiO(3) Heterostructure Driven by Polar Field‐Assisted Oxygen Vacancy Formation at the Surface

The origin of 2D electron gas (2DEG) at LaAlO(3)/SrTiO(3) (LAO/STO) interfaces has remained highly controversial since its discovery. Various models are proposed, which include electronic reconstruction via surface‐to‐interface charge transfer and defect‐mediated doping involving cation intermixing or oxygen vacancy (V (O)) formation. It is shown that the polar field‐assisted V (O) formation at the LAO/STO surface plays critical roles in the 2DEG formation and concurrent structural transition. Comprehensive scanning transmission electron microscopy analyses, in conjunction with density functional theory calculations, demonstrate that V (O) forming at the LAO/STO surface above the critical thickness (t (c)) cancels the polar field by doping the interface with 2DEG. The antiferrodistortive (AFD) octahedral rotations in LAO, which are suppressed below the t (c), evolve with the formation of V (O) above the t (c). The present study reveals that local symmetry breaking and shallow donor behavior of V (O) induce the AFD rotations and relieve the electrical field by electron doping the oxide heterointerface.