Atomic Force Spectroscopy on Ionic Liquids

Ionic liquids have become of significant relevance in chemistry, as they can serve as environmentally-friendly solvents, electrolytes, and lubricants with bespoke properties. In particular for electrochemical applications, an understanding of the interface structure between the ionic liquid and an electrified interface is needed to model and optimize the reactions taking place on the solid surface. As with ionic liquids, the interplay between electrostatic forces and steric effects leads to an intrinsic heterogeneity, as the structure of the ionic liquid above an electrified interface cannot be described by the classical electrical double layer model. Instead, a layered solvation layer is present with a structure that depends on the material combination of the ionic liquid and substrate. In order to experimentally monitor this structure, atomic force spectroscopy (AFS) has become the method of choice. By measuring the force acting on a sharp microfabricated tip while approaching the surface in an ionic liquid, it has become possible to map the solvation layers with sub-nanometer resolution. In this review, we provide an overview of the AFS studies on ionic liquids published in recent years that illustrate how the interface is formed and how it can be modified by applying electrical potential or by adding impurities and solvents.