Strong correlations between electrons, spins and lattices--stemming from strong hybridization between transition metal d and oxygen p orbitals--are responsible for the functional properties of transition metal oxides. Artificial oxide heterostructures with chemically abrupt interfaces provide a platform for engineering bonding geometries that lead to emergent phenomena. Here we demonstrate the control of the oxygen coordination environment of the perovskite, SrRuO3, by heterostructuring it with Ca0.5Sr0.5TiO3 (0-4 monolayers thick) grown on a GdScO3 substrate. We found that a Ru-O-Ti bond angle of the SrRuO3 /Ca0.5Sr0.5TiO3 interface can be engineered by layer-by-layer control of the Ca0.5Sr0.5TiO3 layer thickness, and that the engineered Ru-O-Ti bond angle not only stabilizes a Ru-O-Ru bond angle never seen in bulk SrRuO3, but also tunes the magnetic anisotropy in the entire SrRuO3 layer. The results demonstrate that interface engineering of the oxygen coordination environment allows one to control additional degrees of freedom in functional oxide heterostructures.

For perovskite oxides, ABO3, slight octahedral distortions have close links to functional properties. While perovskite oxide heterostructures offer a good platform for controlling functionalities, atomistic understanding of octahedral distortion at the interface has been a challenge as it requires precise measurements of the oxygen atomic positions. Here we demonstrate an approach to clarify distortions at an atomic level using annular bright-field imaging in aberration-corrected scanning transmission electron microscopy, which provides precise mappings of cation and oxygen atomic positions from distortion-minimized images. This technique revealed significant distortions of RuO6 and ScO6 octahedra at the heterointerface between a SrRuO3 film and a GdScO3 substrate. We also found that structural mismatch was relieved within only four unit cells near the interface by shifting the oxygen atomic positions to accommodate octahedral tilt angle mismatch. The present results underscore the critical role of the oxygen atom in the octahedral connectivity at the perovskite oxide heterointerface.

Thickness‐dependent structure–property relationships in strained SrRuO3 thin films on GdScO3 (GSO) substrates are reported. The film is found to have epitaxially stabilized crystal structures that vary with the film thickness. Below 16 nm, the √2apc × √2apc × 2apc monoclinic structure is stabilized while above 16 nm the film has the apc × 2apc × apc tetragonal structure. The thickness‐dependent structural changes are ascribed to the substrate‐induced modification in the RuO6 octahedral rotation pattern, which highlights the significance of the octahedral rotations for the epitaxial strain accommodation in the coherently‐grown films. Close relationships between the structural and physical properties of the films are also found. The monoclinic film has the uniaxial magnetic easy axis 45° away from the [110]GSO direction while the tetragonal film has the one that lies along the in‐plane [1–10]GSO direction. The results demonstrate that the octahedral rotations in the strained perovskite oxide thin films are a key factor for determining their structure phases and physical properties.