On the Contrasting Effect Exerted by a Thin Layer of CdS against the Passivation of Silver Electrodes Coated with Thiols

The passivation of metal electrodes covered by self-assembled monolayers of long-chain thiols is well known. The disappearance of the voltammetric peak of redox species in solution is a classical test for the formation of full layers of thiols. Similar studies on semiconductors are still very limited. We used silver surfaces covered by an ultrathin layer of CdS as substrate for self-assembling of n-hexadecanethiol (C16SH), and we compared the experimental results with those obtained by using the bare silver surface as substrate. The strong insulating effect of C16SH deposited on Ag(III) is shown by the inhibition of the voltammetric peak of Ru(NH3)63+/2+. On the contrary, the voltammogram obtained on CdS-covered Ag(III) is very similar to that obtained on the bare Ag(III) electrode, thus suggesting that the presence of CdS exerts a contrasting effect on the passivation of the silver electrode. A crucial point of our work is to demonstrate the effective formation of C16SH monolayers on Ag(III) covered by CdS. The formation of full layers of C16SH was strongly suggested by the inhibition of the stripping peak of Cd from the CdS deposit covered by C16SH. The presence of C16SH was confirmed by electrochemical quartz crystal microbalance (EQCM) measurements as well as by Auger electron spectroscopy (AES) analysis.