Nanoscale Intelligent Imaging Based on Real-Time Analysis of Approach Curve by Scanning Electrochemical Microscopy

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Analytical Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.analchem.9b02361.Scanning electrochemical microscopy (SECM) enables high-resolution imaging by examining the amperometric response of an ultramicroelectrode tip near a substrate. Spatial resolution, however, is compromised for non-flat substrates, where distances from a tip far exceed the tip size to avoid artifacts caused by the tip–substrate contact. Herein, we propose a new imaging mode of SECM based on real-time analysis of approach curve to actively control nanoscale tip–substrate distances without contact. The power of this software-based method is demonstrated by imaging an insulating substrate with step edges using standard instrumentation without combination of another method for distance measurement, e.g., atomic force microscopy. An ~500 nm-diameter Pt tip approaches down to ~50 nm from upper and lower terraces of a 500 nm-height step edge, which are located by real-time theoretical fitting of experimental approach curve to ensure the lack of electrochemical reactivity. The tip approach to step edge can be terminated at