Order beyond a monolayer: the story of two 4,4’-bipyridine layers on the Sb(111) | ionic liquid interface

The interface between semi-metallic Sb(111) electrode and ionic liquid with 4,4’-bipyridine addition has been studied. Using in situ scanning tunnelling microscopy and electrochemical impedance spectroscopy, the desorption of 4,4’-bipyridine was demonstrated and a dense underlying structure, formed below a sparse self-assembled monolayer, was visualized. The first SAM layer in contact with the electrode consisted of tightly packed ordered rows, which fine structure has been identified with density functional theory calculations supported by machine learning. The second SAM layer, on top of the first, is characterised by low surface concentration and its unit cell was obtained experimentally. The detection of two separate adsorbed layers indicates that the ordering of organic molecules could extend well beyond the monolayer on the electrode’s surface. These insights are of fundamental and practical importance in the development of nanoelectronic devices.