Manipulating Molecular Self-Assembly Process at the Solid-Liquid Interface Probed by Scanning Tunneling Microscopy

The phenomenon of ordered self-assembly on solid substrates is a topic of interest in both fundamental surface science research and its applications in nanotechnology. The regulation and control of two-dimensional (2D) self-assembled supra-molecular structures on surfaces have been realized through applying external stimuli. By utilizing scanning tunneling microscopy (STM), researchers can investigate the detailed phase transition process of self-assembled monolayers (SAMs), providing insight into the interplay between intermolecular weak interactions and substrate-molecule interactions, which govern the formation of molecular self-assembly. This review will discuss the structural transition of self-assembly probed by STM in response to external stimuli and provide state-of-the-art methods such as tip-induced confinement for the alignment of SAM domains and selective chirality. Finally, we discuss the challenges and opportunities in the field of self-assembly and STM.