Nanopatterning of Cu-Ligated Mercaptoalkanoic Acid Multilayers on Si Substrates via Atomic Force Lithography

Chemical self-assembly has garnered tremendous interest as a tool for generating nanometer-scale structures and devices. Organosilane self-assembled monolayers (SAMs) are of particular interest because of their ability to assemble on a wide range of substrates with varied chemical functionalities. Nanoshaving, an atomic force lithographic technique, has been demonstrated as a method to generate nanopatterns of organosilane SAMs. However, this method requires extremely high force setpoints, which rapidly dulls atomic force microscopy tips and degrades the resolution of the resulting nanopattern. In this work, we utilize Cu-ligated mercaptohexadecanoic acid (MHDA) multilayers to circumvent this limitation. Initially, a 10-undecenyltrichlorosilane (UTS) SAM is assembled onto a Si substrate, and the terminal olefin groups of the UTS SAM are oxidized to carboxyl groups. Subsequently, a Cu-ligated MHDA multilayer is assembled via the sequential deposition of Cu2+ ions and MHDA molecules. The interface between the oxidized UTS SAM and Cu-ligated MHDA multilayer serves as a natural low force breakpoint for nanoshaving. We demonstrate that the resulting nanopatterns can function as a chemical resist to fabricate metal nanostructures