SECM is a powerful scanning probe technique that maps localized electrochemical activity. It works by positioning an ultramicroelectrode (UME) probe ↗ near a substrate surface in an electrolyte solution. The probe is polarized to drive a redox reaction of an electrochemical active species present in the solution. As the probe scans across the surface in the X-Y plane, the measured current reflects local variations in reactivity, conductivity, or topography.
One of the most common modes in SECM is the feedback mode. In this mode, the electrolyte contains a free-diffusing reversible redox mediator that undergoes electrochemical conversion at the SECM probe in a diffusion-controlled manner. As the probe approaches a conductive substrate, the mediator, oxidized or reduced at the polarized probe, is regenerated at the substrate and diffuses back to the probe, increasing the probe current (positive feedback). In contrast, when approaching an insulating substrate, the surface blocks the mediator diffusion to the probe, reducing the current (negative feedback).
Beyond amperometric feedback imaging, SECM systems support, among others, generation-collection mode, potentiometric imaging, and redox competition mode.