A Paradigm Shift from 2D to 3D: Surface Supramolecular Assemblies and Their Electronic Properties Explored by Scanning Tunneling Microscopy and Spectroscopy

Exploring supramolecular architectures at surfaces plays an increasingly important role in contemporary science, especially for molecular electronics. A paradigm of research interest in this context is shifting from 2D to 3D that is expanding from monolayer, bilayers, to multilayers. Taking advantage of its high‐resolution insight into monolayers and a few layers, scanning tunneling microscopy/spectroscopy (STM/STS) turns out a powerful tool for analyzing such thin films on a solid surface. This review summarizes the representative efforts of STM/STS studies of layered supramolecular assemblies and their unique electronic properties, especially at the liquid–solid interface. The superiority of the 3D molecular networks at surfaces is elucidated and an outlook on the challenges that still lie ahead is provided. This review not only highlights the profound progress in 3D supramolecular assemblies but also provides researchers with unusual concepts to design surface supramolecular structures with increasing complexity and desired functionality. Supramolecular assemblies shifting from 2D to 3D revealed by scanning tunneling microscopy/spectroscopy (STM/STS) provide insights into the design of supramolecular architectures with increasing complexity and desired functionality. This review summarizes STM/STS studies of several molecular systems with an emphasis on the unique characteristics and electronic properties of multilayered assembled structures at the liquid–solid interface.