From Functional Group Ensembles to Single Molecules: Scanning Force Microscopy of Supramolecular and Polymeric Systems

Surfaces in supramolecular and polymeric systems were characterized by scanning force microscopy (SFM) using probe tips functionalized with self-assembled monolayers (SAMs). This approach allows one to control the forces between tip and surface by immobilizing suitable molecules, which expose selected functional groups, onto gold-coated probes. The objective of this Thesis work was the extension of SFM with SAM-functionalized probes (so-called "chemical force microscopy", CFM) to technologically relevant surfacetreated polymers and elastomers with the ultimate aim of laterally resolved detection of functional group distributions on a sub-100 nm level. In measurements of interaction forces between a few or even individual molecules in supramolecular systems the transition from studying continuum to studying non-continuum properties was also attempted. In situ measurements of reaction kinetics using "inverted CFM" on a scale of 10 - 100 molecules were achieved. Furthermore, interactions between ensembles of functional groups and individual molecules were studied and provided fundamental insight into functional group distributions on polymer surfaces as well as rupture forces of individual host-guest complexes.