Influence of electrode size and geometry on electrochemical experiments with combined SECM-SFM probes

Gold electrodes integrated into silicon scanning force microscopy (SFM) probes allow the acquisition of spatially correlated data for sample morphology (via SFM) and local electrochemical reactivity via scanning electrochemical microscopy (SECM). The lateral resolution of both techniques is controlled by different properties of the integrated probes. The topographic tracking provided by the SFM mechanism allows the realization of very small working distances for the SECM measurements. Microfabrication technology was used in order to reduce the size of the active electrode area of the tip into the sub-100 nm regime. The functionality of the probes was tested using electrochemical methods. Experiments revealed that the response could be quantitatively compared to numerical simulation. The low working distance, in combination with the small size of the active electrode area, allows for high lateral resolution in the SECM images. This is illustrated with different model substrates that cover a range of different rate constants and illustrate the dependence of the SECM contrast on the local kinetics of the sample in the sub-micrometre size range.