Mastery of order-disorder processes in highly nonequilibrium nanostructured oxides has significant implications for the development of emerging energy technologies. However, we are presently limited in our ability to quantify and harness these processes at high spatial, chemical, and temporal resolution, particularly in extreme environments. Here, we describe the percolation of disorder at the model oxide interface LaMnO₃/SrTiO₃, which we visualize during in situ ion irradiation in the transmission electron microscope. We observe the formation of a network of disorder during the initial stages of ion irradiation and track the global progression of the system to full disorder. We couple these measurements with detailed structural and chemical probes, examining possible underlying defect mechanisms responsible for this unique percolative behavior.

Perovskite titanates such as SrTiO3 (STO) exhibit a wide range of important functional properties, including ferroelectricity and excellent photocatalytic performance. The wide optical band gap of titanates limits their use in these applications; however, making them ill-suited for integration into solar energy harvesting technologies. Our recent work has shown that by doping STO with equal concentrations of La and Cr, we can enhance visible light absorption in epitaxial thin films while avoiding any compensating defects. In this work, we explore the optical properties of photoexcited carriers in these films. Using spectroscopic ellipsometry, we show that the Cr3+ dopants, which produce electronic states immediately above the top of the O 2p valence band in STO reduce the direct band gap of the material from 3.75 eV to 2.4-2.7 eV depending on doping levels. Transient reflectance spectroscopy measurements are in agreement with the observations from ellipsometry and confirm that optically generated carriers are present for longer than 2 ns. Finally, through photoelectrochemical methylene blue degradation measurements, we show that these co-doped films exhibit enhanced visible light photocatalysis when compared to pure STO.

The behavior of polar LaMnO3 (LMO) thin films deposited epitaxially on nonpolar SrTiO3(001) (STO) is dictated by both the LMO/STO band alignment and the chemistry of the Mn cation. Using in situ X-ray photoelectron spectroscopy, the valence band offset (VBO) of LMO/STO heterojunctions is directly measured as a function of thickness, and found that the VBO is 2.5 eV for thicker (≥3 u.c.) films. No evidence of a built-in electric field in LMO films of any thickness is found. Measurements of the Mn valence by Mn L-edge X-ray absorption spectroscopy and by spatially resolved electron energy loss spectra in scanning transmission electron microscopy images reveal that Mn2+ is present at the LMO surface, but not at the LMO/STO interface. These results are corroborated by density functional theory simulations that confirm a VBO of ≈2.5 eV for both ideal and intermixed interfaces. A model is proposed for the behavior of polar/nonpolar LMO/STO heterojunctions in which the polar catastrophe is alleviated by the formation of oxygen vacancies at the LMO surface.