Manipulating single oxygen at Cu_(2)O-island surfaces through thermomechanical coupling  

力-热耦合效应对Cu_(2)O氧化岛表面单原子氧的调控

作　　者：Huanhuan Yang Xiao Jiang Zhihao Wang Hanpu Liang Xie Zhang Pengfei Guan 杨欢欢;姜肖;王智灏;梁汉普;张燮;管鹏飞(Materials and Energy Division,Beijing Computational Science Research Center,Beijing 100193,China;School of Materials Science and Engineering,Northwestern Polytechnical University,Xi’an 710072,China)

机构地区：[1]Materials and Energy Division,Beijing Computational Science Research Center,Beijing 100193,China [2]School of Materials Science and Engineering,Northwestern Polytechnical University,Xi’an 710072,China

出　　处：《Science China Materials》2024年第10期3288-3297,共10页中国科学（材料科学）（英文版）

基　　金：supported by the National Natural Science Foundation of China(U2230402,T2325004).

摘　　要：Single oxygen diffusion event,the most favorable rate-limiting process of epitaxial Cu_(2)O oxide-island layerby-layer growth kinetics,may lead to oxygen defects due to thermomechanical coupling.However,the formation rules of oxygen defects remain unclear,preventing the realization of controllable oxygen defects on oxide-island surfaces.Here,we utilize the first-principles method to investigate the formation rules of intrinsic oxygen defects in the surface layers of prototypical metal-oxide(Cu_(2)O)surfaces under thermomechanical coupling effects.We establish the thermodynamic phase diagram for oxygen-defect-modulated Cu_(2)O surfaces,enabling the prediction of the growth of oxide islands during Cu oxidation,which aligns closely with in-situ environmental transmission electron microscopy(ETEM)experiment observations.By exploring the strain-modulated phase diagrams,we propose a potential strategy for controlling the type and concentration of oxygen defects on oxide-island surfaces.Our findings provide an effective approach to theoretically understanding the oxidation process of metal surfaces,thus enabling the computational design of high-performance corrosion-resistant surfaces.单原子氧的扩散,是外延Cu_(2)O氧化岛逐层生长动力学中的热力学决速步,其中力-热耦合效应会导致氧缺陷的出现.而氧缺陷在氧化岛表面的形成机制及其调控仍需进一步的研究.基于第一性原理模拟,本文以典型的金属氧化物Cu_(2)O为研究对象,系统地研究了力-热耦合效应下,表面不同嵌入深度的本征氧缺陷的热力学形成行为.通过构建关于氧缺陷调控的热力学相图,预测了Cu表面氧化过程中Cu_(2)O氧化岛的生长机制,其与原位环境透射电子显微镜(ETEM)的实验观测具有较好的一致性.通过引入应力调控的氧缺陷的热力学相图,实现了对氧化岛表面上氧缺陷的类型和浓度的调控.本文为理解金属表面的逐层氧化行为提供了理论支持,并为设计高性能的抗腐蚀氧化物表面提供了调控方案.

关 键 词：first-principles calculations Cu_(2)O-island surfaces oxygen defects biaxial strains thermodynamic phase diagram 

分 类 号：TQ131.21[化学工程—无机化工]