Cooperative evolution of polar distortion and nonpolar rotation of oxygen octahedra in oxide heterostructures

Polarity discontinuity across LaAlO(3)/SrTiO(3) (LAO/STO) heterostructures induces electronic reconstruction involving the formation of two-dimensional electron gas (2DEG) and structural distortions characterized by antiferrodistortive (AFD) rotation and ferroelectric (FE) distortion. We show that AFD and FE modes are cooperatively coupled in LAO/STO (111) heterostructures; they coexist below the critical thickness (t(c)) and disappear simultaneously above t(c) with the formation of 2DEG. Electron energy-loss spectroscopy and density functional theory (DFT) calculations provide direct evidence of oxygen vacancy (V(O)) formation at the LAO (111) surface, which acts as the source of 2DEG. Tracing the AFD rotation and FE distortion of LAO reveals that their evolution is strongly correlated with V(O) distribution. The present study demonstrates that AFD and FE modes in oxide heterostructures emerge as a consequence of interplay between misfit strain and polar field, and further that their combination can be tuned to competitive or cooperative coupling by changing the interface orientation.