A comparative study on the adsorption of buthanedithiol (BDT), hexanedithiol (HDT), and nonanedithiol (NDT) on Au(111) from ethanolic and n-hexane solutions and two different preparation procedures is presented. SAM characterization is based on reflection-absorption infrared spectroscopy, electrochemistry, X-ray photoelectron spectroscopy, and time of flight direct recoil spectroscopy. Results indicate that one can obtain a standing-up phase of dithiols and that the amount of the precursor lying-down phase decreases from BDT to NDT, irrespective of the solvent and self-assembly conditions. A good ordering of the hydrocarbon chains in the standing-up configuration is observed for HDT and NDT when the system is prepared in degassed n-hexane with all operations carried out in the dark. Disulfide bridges at the free SH terminal groups are formed for HDT and to a lesser extent for NDT prepared in ethanol in the presence of oxygen, but we found no evidence of ordered multilayer formation in our experiments. No disulfides were observed for BDT that only forms the lying-down phase. Our results demonstrate the key role of the chain length and the procedure (solvent nature and oxygen presence) in controlling the surface structure and chemistry of SAMs dithiols on Au(111).

We present a study of the growth and thermal stability of hexanethiol (C6) films on GaAs(110) by direct recoil spectroscopy with time-of-flight analysis. We compare our results with the better known case of C6 adsorption on Au(111). In contrast to the two-step adsorption kinetics observed for Au surfaces after lengthy exposures, data for C6 adsorption on the GaAs(110) surface are consistent with the formation of a single dense phase of C6 molecules at lower exposures. On the contrary, in solution preparation, dense phases can only be obtained on GaAs for long alkanethiols and after lengthy immersions. The C6 layer has a first desorption peak at 325 K, where partial desorption of the alkanethiol molecules takes place. Fits to the desorption curves result in a 1 eV adsorption energy, in agreement with a chemisorption process. Increasing the temperature to 500 K results in the S-C bond scission with only S remaining on the GaAs(110) surface. The possibility of forming dense, short-alkanethiol layers on semiconductor surfaces from the vapor phase could have a strong impact for a wide range of self-assembled monolayer applications, with only minimal care not to surpass room temperature once the layer has been formed in order to avoid molecular desorption.