Analysis of atomic force microscope pull-off forces for gold surfaces portraying nanoscale roughness and specific chemical functionality

Pull-off force measurements were carried out between gold-coated atomic force microscope (AFM) cantilever tips modified with self-assembled monolayers (SAMs) of thiols and similar SAMs prepared on gold-coated silicon wafer surfaces in air with a relative humidity level less than 15%. The gold sputtered silicon wafer substrate formed a granular morphology with dimensions of 30-50 nm. The radii of curvatures for the two different cantilever tips used in this study were 32 nm and 53 nm. Pull-off force results were analyzed using the Derjaguin-Muller-Toporov (DMT) contact mechanics theory to determine both surface free energy (γ) for OH, CH3, CO2H and NH2-terminated monolayers and the resultant work of adhesion (W A) between SAMs. The analysis took into account the coarse morphology of the gold coating. It was found that the γ and W A values determined with the AFM technique approached similar thermodynamic parameters as calculated from the Lifshitz-van der Waals/Lewis acid-base interaction theory using advan...