(72b) Chemical Imaging and Interaction Quantification On the Surface Oxide Layer of Cu(100) Using High-Resolution Atomic Force Microscopy

Chemistry is governed by the interactions between atoms and molecules. On surfaces, chemical forces extending into the vacuum direct the behavior of many scientifically and technically important phenomena including surface catalysis. Therefore, it would be useful to map and quantify the interactions between a catalytically active surface and a probe with atomic resolution in order to study the role and effectiveness of various surface defects such as vacancies, impurities, steps, kinks, and domain boundaries as active sites. An ability to discriminate between different chemical species on the sample surface would offer further insight. In this talk, we will show with the example of an oxygen-reconstructed copper (100) surface that much of this information can be derived from combining the new method of three-dimensional atomic force microscopy (3D-AFM), a variant of noncontact atomic force microscopy, with scanning tunneling microscopy. The surface oxide layer of Cu(100) features domain boundaries and a distinct structure of the Cu and O sublattices that is ideally suited for such model investigations. While different tips show different chemical contrasts, 3D data sets enable site-specific quantification of force interactions and tunneling currents. In order to clarify the different contrast modes data, DFT total-energy calculations and Non-equilibrium Green's Function (NEGF) methods for electronic transport have been used to determine the interaction and the tunneling current for a large set of tip models. These calculations provide insight into (1) the fundamentals of contrast formation in this experimental technique and (2) into the correlation between tip-sample forces and local chemical reactivity, factors that are essential for the further development and application of this novel approach to characterizing catalytic activity.