Abstract
Temperature-programmed desorption (TPD) of self-assembled monolayers (SAMs) on gold is investigated by using in parallel mass spectrometry (MS) and infrared reflection−absorption spectroscopy (IRAS). Monolayers formed by HS(CH2)n−OH (n = 18, 22) and HS(CH2)15−CONH−(CH2CH2O)−H (EG1) are compared to reveal the influence of specifically introduced hydrogen-bonding groups on their thermal stability. The overall desorption process of the above molecules is found to occur in two main steps; a disordering of the alkyl chains followed by a complex series of decomposition/desorption reactions. The final step of the process involves desorption of sulfur from different chemisorption states. The amide-group-containing SAM, which is stabilized by lateral hydrogen bonds, displays a substantial delay of the alkyl chain disordering by about 50 K, as compared to the linear chain alcohols HS(CH2)n−OH. Moreover, the decomposition of the alkyls and the onset of sulfur desorption occur at a temperature that is higher by appro...
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