Influence of Temperature on the Nanoadhesion of a Methyl-Terminated Thiol Monolayer: A New Insight with High-Rate Dynamic Force Spectroscopy.

Abstract

Alkanethiols form stable, homogeneous, and well-organized self-assembled monolayers and can be used as lubricants in micro- and nanodevices when sufficiently hydrophobic and resistant to sudden temperature changes. In this paper, we demonstrate a new analysis method which provides a deep physical insight into adhesive interactions and their temperature dependencies at the single molecule level. We have focused on the adhesion between a silicon nitride tip and a 1-decanethiol self-assembled monolayer in the temperature range from 25 to 85 °C. We performed dynamic force spectroscopy measurements and applied theoretical models of adhesive-mechanical interactions and thermally activated unbinding to obtain detailed information on the adhesive interactions. The parameters of the interaction potential describing a single adhesive bond were calculated, and their temperature dependence was discussed. Although the changes of the adhesion force versus temperature are significant and nonmonotonic, the energy of the activation barrier of a single adhesive bond appears temperature independent. We attribute observed changes in the position of the activation barrier to the interplay between the rupture and rebinding of adhesive bonds, as well as to thermal reorganization, in particular the change of the tilt angle of thiol molecules in the self-assembled monolayer.