Electrochemical metal dissolution reaction is a fundamental process in various critical technologies, including metal anode batteries and nanofabrication. However, experimentally revealing the kinetics and dynamics of active sites of metal dissolution reactions is challenging. Herein, we investigate metal dissolution on near-perfect single-crystal surfaces of Ag within regions of a few hundred nanometers isolated by scanning electrochemical cell microscopy (SECCM). Potential oscillation is observed under constant current conditions for dissolution. The one-to-one correspondence between the dissolution charge and the geometry of the dissolution pit from colocalized imaging allows ambiguous correlation, which suggests that each oscillation cycle corresponds to the dissolution of one atomic layer. The oscillation behavior is further explained in a kinetic model, which reveals that the oscillation comes from the dynamic evolution of the number of different active sites as the dissolution progresses on each atomic layer. In addition to the fundamental interest, the ability to observe layer-by-layer dissolution in electrochemical measurements suggests a potential pathway for developing electrochemical atomic layer etching for fabricating structures and devices with atomic precision.

中文翻译：

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低缺陷 Ag 上原子层溶解的动力学和动力学


电化学金属溶解反应是各种关键技术的基本过程，包括金属负极电池和纳米制造。然而，通过实验揭示金属溶解反应活性位点的动力学和动力学具有挑战性。在此，我们通过扫描电化学细胞显微镜 （SECCM） 研究了在几百纳米隔离的区域内 Ag 近乎完美的单晶表面上的金属溶解。在恒流条件下观察到溶解的电位振荡。溶出电荷与共定位成像的溶出几何形状之间的一一对应关系允许模棱两可的相关性，这表明每个振荡周期对应于一个原子层的溶出。动力学模型进一步解释了振荡行为，该模型揭示了振荡来自随着每个原子层上的溶解进展，不同活性位点数量的动态演变。除了基本利益之外，在电化学测量中观察逐层溶解的能力为开发电化学原子层蚀刻以制造具有原子精度的结构和设备提供了一条潜在的途径。