XAS and XPS Characterization of Monolayers Derived from a Dithiol and Structurally Related Disulfide-Containing Polyamides

X-ray absorption spectroscopy and X-ray photoemission spectroscopy have been used to examine sulfur−gold bond formation in monolayers derived from a dithiol monomer and related disulfide-containing polyamides. These compounds were designed to allow the molecules to adsorb to gold through two terminal sulfurs, forming surface-attached loops. Element and site-specific density of unoccupied electronic states were probed by X-ray absorption spectroscopy at the C 1s, N 1s, O 1s (K-edge), and S 2p (L2,3-edge) absorption edges. Photoemission measurements of the C 1s, N 1s, O 1s, and S 2p core lines were also used to estimate relative coverage, to confirm layer formation, and to evaluate chemical bonding of the monomer and polyamide to the gold-coated substrates. In the case of the dithiol monomer, the spectroscopic evidence clearly shows that most of the molecules adsorb through a single thiol end. The disulfide-containing precursors, in contrast to the monomer, attach to the surface through both sulfurs to form the anticipated surface-attached loop.