Understanding the Two-Dimensional Mixing Behavior of 1-Naphthalenethiol and Octanethiol

A two-dimensional (2D) mixture in the form of a self-assembled monolayer composed of two distinct organothiol compounds was created by sequentially depositing 1-naphthalenethiol (1NT) and octanethiol (OT) on a gold surface. By varying the sequence of deposition, two mixed surface systems were created. The surface structure of the resulting mixed monolayer was characterized with Scanning Tunneling Microscopy (STM) and showed surface disorder across all investigated domains. Elemental analysis was carried out with X-ray Photoelectron Spectroscopy (XPS) and indicated that the 1NT monolayer was prone to significant oxidation. Reductive desorption (RD) was used to characterize the binding strength and electrochemical environments of the molecular components in the mixture, and confirmed disordered molecular layers. Due to the presence of oxidized species in the 1NT monolayer, 1NT was displaced by OT resulting in a novel surface structure composed of either OT or 1NT. Monolayers of OT that were exposed to a solution of 1NT resulted in disordered surface structures with a significant amount of gold vacancy islands. To date, there is no experimental phase diagram explaining the chemical behavior of two-dimensional mixtures. This study addresses the need for an experimental understanding of the phase behavior of mixed organothiol self-assembled monolayers (SAMs).