Understanding
the impact of the intricate morphology and surface
chemistry of ZnO nanorod arrays on their interactions with polyelectrolyte
polymers is crucial for the development of nascent ZnO-based adhesion-promoting
materials. AFM-based single molecule force spectroscopy was applied
for the analysis of the adsorption of poly(acrylic acid) (PAA) on
zinc oxide (ZnO) film covered stainless steel substrates in aqueous
electrolytes at pH 7. Based on the electrodeposition process, the
morphology of zinc oxide films could be varied ranging from platelet-like
crystals to nanorods. This approach allowed for the morphology dependent
analysis of macromolecular adsorption processes on complex ZnO nanostructures
which have diverse applications in the field of adhesion-promoting
thin films. The surface chemical composition, as determined by X-ray
photoelectron spectroscopy, could be correlated to the AFM-based desorption
studies. Only equilibrium desorption events (plateaus), centered at
42 pN, were observed on mirror polished, preconditioned stainless
steel. However, for platelet-like ZnO films, the poly(acrylic acid)
desorption showed a mixture of rupture events (mean rupture forces
of about 350 pN) and equilibrium desorption, while ZnO nanorod structures
showed solely rupture events with mean rupture forces of about 1300
pN. These results indicate that simultaneous multiple ruptures of
carboxylate–zinc bonds occur due to the macromolecular coordination
of poly(acrylic acid) to the ZnO nanorods. The analysis of the interfacial
adhesion processes is further supported by the dwell time dependence
of desorption processes.