Electron-Induced Formation of C 2 on Si(100) from Acetylene and Ethylene

Abstract Hydrogen Desorption Lithography on Si(100) demonstrates the ability of the Scanning Tunneling Microscope (STM) to create functional atomic-scale structures and devices. The dehydrogenation of adsorbed molecules represents a potential complementary technique that has received little attention. For example, formation of C2 could introduce local strain or act as a center for subsequent reactions and would inform positionally controlled mechanosynthesis, an approach with vast potential in surface patterning and functionalization. Here, we studied the electron-induced dehydrogenation of acetylene and ethylene on Si(100) at 4 K using STM. Excitation of acetylene at ≥+3.2 V induces configurational switching, including to a new sublayer-bonded geometry previously predicted to be an adsorption precursor, as well as migration and desorption. Excitation also induces dehydrogenation to C2. Switching between three observed C2 configurations can be induced by excitation at ≥+4.2 V. Simulations using density functional theory reproduced the experimental images based on the choice of functional, dimer-buckling averaging, and the inclusion of diffuse basis functions. In addition, dehydrogenation could be induced using field-emitted electrons on a scale ranging from a single molecule to a radius of >10 nm. These observations highlight the potential of carbon dehydrogenation as an additional tool in Atomically Precise Fabrication (APF).