Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing.
Yang, N., Doria, S., Kumar, A., Jang, J. H., Arruda, T. M., Tebano, A., Jesse, S., Ivanov, I. N., Baddorf, A. P., Strelcov, E., Licoccia, S., Borisevich, A. Y., Balestrino, G., & Kalinin, S. V. (2014). Water-mediated electrochemical nano-writing on thin ceria films. Nanotechnology, 25(7). https://doi.org/10.1088/0957-4484/25/7/075701