Observing Real-Time Formation of Self-Assembled Monolayers on Polycrystalline Gold Surfaces with Scanning Electrochemical Cell Microscopy.

Self-assembled monolayers (SAMs) of alkanethiols on gold have become a central focus of controllable surface chemistry because they can be easily formed from the solution phase and characterized using various techniques. Understanding the formation processes occurring at a nanoscale level is crucial to form defect-free SAMs for tailored applications in bio- and nanotechnology. Although many reports study and characterize SAMs after they are formed on gold surfaces, typical methods have not extensively studied the SAM formation process at the nanoscale. This paper focuses on the formation of defect-free SAMs and elucidates the formation mechanism occurring at the nanoscale level during the formation process. Exploiting the strength of scanning electrochemical cell microscopy, we monitored SAM formation via a soluble redox reporter on a polycrystalline gold foil using voltammetric and amperometric techniques. We formed SAMs by varying the concentration of 3-mercapto-1-propanol [HS(CH)OH], 6-mercapto-1-hexanol [HS(CH)OH], and 9-mercapto-1-nonanol [HS(CH)OH] to determine the effects of the thiol chain length, concentration, and location on the substrate (grain boundaries) on monolayer formation. We observed real-time changes in the quasisteady-state current of our redox reporter during the self-assembly process. Importantly, we formed defect-free SAMs at the nanoscale level using different concentrations of HS(CH)OH and HS(CH)OH and found that SAM formation at the nanoscale is concentration-dependent and varies when at a boundary between two crystal grains.