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The presence of mobile ions complicates the implementation of voltage-modulated scanning probe microscopy techniques such as Kelvin probe force microscopy (KPFM). Overcoming this technical hurdle, however, provides a unique opportunity to probe ion dynamics and electrochemical processes in liquid environments and the possibility to unravel the underlying mechanisms behind important processes at the solid-liquid interface, including adsorption, electron transfer and electrocatalysis. Here we describe the development and implementation of electrochemical force microscopy (EcFM) to probe local bias- and time-resolved ion dynamics and electrochemical processes at the solid-liquid interface. Using EcFM, we demonstrate contact potential difference measurements, consistent with the principles of open-loop KPFM operation. We also demonstrate that EcFM can be used to investigate charge screening mechanisms and electrochemical reactions in the probe-sample junction. We further establish EcFM as a force-based imaging mode, allowing visualization of the spatial variability of sample-dependent local electrochemical properties.

Probing charge screening dynamics and electrochemical processes at the solid–liquid interface with electrochemical force microscopy