Intercalating Single-Atom Metal Centers into an Organic Monolayer with a Full-Sample Coverage

Thiolate self-assembled monolayers (SAMs) have been widely used as a straightforward method to functionalize the surface of a common substrate with selective organic functional groups. Here we describe a process that further introduces isolated metal centers into an organic SAM using solutions of metallic porphyrin so that different organic groups and metal single-atoms can be simultaneously exposed on top of the surface. The entire process employs only common laboratory equipment and mild-temperature (<100 °C) incubation to create a full-sample (>cm²) SAM coverage. Each step in this process is closely monitored and discussed using nm-scale scanning tunneling microscopy (STM) images. This work can be straightforwardly adopted by research groups interested in such a diversely customizable surface but without access to a vacuum-based deposition technology. The porphyrin molecules are shown to intercalate among closely packed thiolate SAM domains, and STM characterization shows that the entire mixed monolayer is stable in an ambient condition. This process also does not involve any tip-assisted desorption or lithography procedure and can thus be applied toward substrates of other shapes beyond a flat surface.