No abstract

In traditional models of heteroepitaxy, the substrate serves mainly as a crystalline template for the thin-film lattice, dictating the initial roughness of the film and the degree of coherent strain. Here, performing in situ surface x-ray diffraction during the heteroepitaxial growth of LaTiO3 on SrTiO3 (001), we find that a TiO2 adlayer composed of the (13×13)R33.7° and (2×2)R45.0° reconstructions is a highly active participant in the growth process, continually diffusing to the surface throughout deposition. The effects of the TiO2 adlayer on layer-by-layer growth are investigated using different deposition sequences and anomalous x-ray scattering, both of which permit detailed insight into the dynamic layer rearrangements that take place. Our work challenges commonly held assumptions regarding growth on TiO2-terminated SrTiO3 (001) and demonstrates the critical role of excess TiO2 surface stoichiometry on the initial stages of heteroepitaxial growth on this important perovskite oxide substrate material.

Control over structure and composition of (ABO) perovskite oxides offers exciting opportunities since these materials possess unique, tunable properties. Perovskite oxides with cobalt B-site cations are particularly promising, as the range of the cation's stable oxidation states leads to many possible structural frameworks. Here, we report growth of strontium cobalt oxide thin films by molecular beam epitaxy, and conditions necessary to stabilize different defect concentration phases. In situ X-ray scattering is used to monitor structural evolution during growth, while in situ X-ray absorption near-edge spectroscopy is used to probe oxidation state and measure changes to oxygen vacancy concentration as a function of film thickness. Experimental results are compared to kinetically limited thermodynamic predictions, in particular, solute trapping, with semiquantitative agreement. Agreement between observations of dependence of cobaltite phase on oxidation activity and deposition rate, and predictions indicates that a combined experimental/theoretical approach is key to understanding phase behavior in the strontium cobalt oxide system.