Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Department of Materials Science and Engineering, Northwestern University , Evanston, Illinois 60208, United States.
ACS Appl Mater Interfaces. 2018 Feb 14;10(6):5949-5958. doi: 10.1021/acsami.7b16970. Epub 2018 Jan 31.
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.
控制(ABO)钙钛矿氧化物的结构和组成提供了令人兴奋的机会,因为这些材料具有独特的、可调的性质。钴 B 位阳离子的钙钛矿氧化物尤其有前途,因为阳离子的稳定氧化态范围导致了许多可能的结构框架。在这里,我们通过分子束外延报告了氧化锶钴薄膜的生长,以及稳定不同缺陷浓度相所需的条件。原位 X 射线散射用于监测生长过程中的结构演变,而原位 X 射线吸收近边光谱用于探测氧化态,并测量氧空位浓度随薄膜厚度的变化。实验结果与动力学受限热力学预测进行了比较,特别是溶质捕获,具有半定量的一致性。钴酸盐相的氧化活性和沉积速率依赖性的观察结果与预测结果之间的一致性表明,结合实验/理论方法是理解锶钴氧化物体系中相行为的关键。