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EC-SPM essentially combines two independent techniques together: electrochemistry and SPM. The electrochemical unit includes a potentiosat and a 3-electrode cell that controls the electrochemical state of the working electrode (usually the sample). The SPM characterizes the surface of the solid electrode with either a passive probe or an active probe. With a passive probe in EC-AFM, the potential of the probe is not controlled. The AFM cantilever acts as an inert probe that monitors the topographic changes of the electrode surface caused by electrochemical processes, using standard AFM imaging modes. On the other hand, with an active probe in EC-STM, a bipotentiostat is used to control the potential of the sample and the probe vs. the same reference electrode. Like a regular STM, the tunneling current between the tip and the sample depends on the potential difference and the distance between the two, and is used as the control signal for STM imaging. With EC-STM, the morphological information of the electrode surface under potential control can be imaged in constant current mode, and the changes of localized electronic state of the electrode surface with electrochemical potential can be studied by current vs. voltage spectroscopy.
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