Thiobis(hexamethyldisilazane) as a new precursor for the deposition of sulfur on gold: A one-step concerted adsorption process

Direct experimental evidence for the deposition of sulfur on gold surfaces using thiobis(hexamethyldisilazane) as a new precursor is provided. The modified surfaces are characterized using cyclic voltammetry, X-ray photoelectron spectroscopy, and scanning tunneling microscopy. XPS and electrochemical results show that the modification process is very fast and that high coverage values are reached within a few minutes. The XPS does not show the initial deposition of fragments of thiobis(hexamethyldisilazane) but only shows the deposition of sulfur even after very short modification times. STM results confirm the formation of dense sulfur films and show the formation of the well-known rectangular structures. Images also show the formation of sulfur multilayers. The electrochemical characteristics of the precursor along with its theoretical investigation and the known chemical reactivity of sulfur transfer agents in organic synthesis rule out the dissociative reductive adsorption process. A concerted adsorption mechanism is proposed and is associated with the concerted cleavage of both SN chemical bonds.