Quantitative analysis of temperature effects in radiation damage of thiolate-based self-assembled monolayers

Following our earlier finding of temperature effects in the radiation damage of self-assembled monolayers (SAMs) we investigated in detail the x-ray-induced modification of aliphatic and aromatic thiolate-based SAMs formed from dodecanethiol and biphenylthiol on gold substrates as representative test systems. For six sample temperatures between 50 and 300 K we measured cross sections and saturation behaviour for the most prominent irradiation-induced reactions, including desorption of hydrocarbon fragments, breaking of the headgroup-substrate bond, and formation of cross-linking networks and secondary bonds of the headgroup atoms within the layer. The results are discussed