Enhancing image quality of scanning electrochemical microscopy by improved probe fabrication and displacement

Abstract

Scanning electrochemical microscopy (SECM) is a powerful tool for its wide applications in determining charge transfer kinetics, imaging chemical reactions and topography, as well as fabricating microstructures at various interfaces and (or) surfaces. Imaging applications, in particular, rely on the natures of SECM probes and the scanning systems to move them in the vicinity of interfaces. While progress has been made in new approaches to tip fabrication, there are few reports on the improvement of the tip positioning system to enhance SECM image quality. We have recently built an advanced SECM setup using a closed-loop scanning system and improved probe fabrication and characterization procedures. Here we will describe this development, as well as the application of these techniques to greatly improve the quality of SECM images. Video micrograph, cyclic voltammograms, and SECM approach curves (current vs. tip–substrate distance) were chosen to characterize probe quality and to determine the ratio of electrode diameter to glass sheath diameter. The SECM setup has a resolution and repeatability of 20 nm in three dimensions (x, y, and z) and can locate and relocate areas of interest precisely after a coarse image. Interdigitated electrode arrays of platinum and gold were first imaged. Image resolution revealed by sharpness of Pt band edges was enhanced by using a 2 µm diameter electrode. Pt or Au band height was found to be around 80–200 nm by fitting the approach curves to the theoretical ones. Imaging conditions such as delay time for a large step size between two succeeding data points were optimized. To test its thermal and temporal stability, the system was then used to image letters, which were printed on a transparency with font bold Courier New and font size 2. Minor drifts were found during the image process up to the experimental length of 8 h and 45 min. Letter thickness was found to be 1.0–1.2 µm. A silicon substrate with an array of square pits spaced apart on 10 µm centers was finally imaged. Good quality images were obtained at various tip–substrate distances even though the squares were just as small, if not smaller, than the tip. The samples were also imaged by AFM for comparison.Key words: scanning electrochemical microscopy, atomic force microscopy, microelectrode fabrication, closed-loop imaging, probe approach curve.