Enhanced thermal stability and structural ordering in short chain n-alkanethiol monolayers on gold probed by vibrational spectroscopy and EQCM

Monolayers of alkanethiols with varied chain lengths, CH₃(CH₂)_nSH where n = 3, 5, and 7, on gold substrates have been prepared by adsorption from (1) neat thiol, (2) millimolar thiol solution in alcohol (conventional method), and (3) potential-controlled adsorption. Reflection absorption infrared spectroscopy (RAIRS) and electrochemical quartz crystal microbalance (EQCM) have been used to characterize the integrity of the monolayers. Methylene and methyl stretching modes along with C–S stretching modes have been used as benchmarks to follow the order–disorder transitions in the monolayer structure, in the temperature range from 25 to 175 °C. Monolayers adsorbed from neat thiol show superior quality in terms of stability and structural arrangement. Short chain thiols with n = 3, 5, and 7 do show substantial stability. The possibility of multilayer formation is ruled out by EQCM studies comparing the frequency and mass change associated with the monolayer desorption. Self-assembled monolayers (SAMs) adsorbed under potential control behave very similarly to the monolayers adsorbed from neat thiol as far as stability and structural orientation are concerned, irrespective of the chain length. The adsorption from neat thiol gets rid of the solvent-induced defects and arrests the propagation of defects under temperature constraints.