Formation Dynamics of Hexadecanethiol Self-Assembled Monolayers on (001) GaAs Observed With Photoluminescence and Fourier Transform Infrared Spectroscopies

The dynamics of hexadecanethiol (HDT) [HS(CH₂)₁₅CH₃] chemisorption and the formation of a self-assembled monolayer (SAM) on the GaAs(001) surface was studied in situ by monitoring the photoluminescence (PL) intensity over a 20 h period. Comparing the PL time series in HDT solution with that of the bare GaAs surface similarly exposed to the ethanol solvent, we observed a two-phased evolution of the associated PL enhancement. Time-commensurate changes in the absorption frequency and intensity of the C–H stretching mode vibrations were then recorded using Fourier transform infrared spectroscopy, supporting that the PL enhancement corresponds directly with known mechanisms of ordered SAM formation. These results highlight the sensitivity with which in situ PL monitoring can reflect surface processes and underscores its potential for use in sensor applications.