Adhesion forces in AFM of redox responsive polymer grafts: Effects of tip hydrophilicity

The adherence between silicon nitride AFM tips and redox-active poly(ferrocenylsilanes) (PFS) grafts on gold was investigated by electrochemical AFM force spectroscopy. Before the adhesion measurements silicon nitride AFM probes were cleaned with organic solvents (acetone and ethanol) or piranha solution. Interestingly, these different AFM tip cleaning procedures drastically affected the observed adhesion forces. Water contact angle measurements on the corresponding AFM probe chips showed that piranha treatment resulted in a significant increase of AFM probe chip surface hydrophilicity compared to the organic solvent treatment. Obviously this hydrophilicity change caused drastic, even opposite changes in the tip-PFS adhesive force measurement upon electrode potential change to reversibly oxidize and reduce the PFS grafts. Our findings are of pivotal importance for AFM tip adhesion measurements utilizing standard silicon nitride AFM tips. Probe hydrophilicity must be carefully taken into consideration and controlled.