Prev. Article Next Article Table of Contents

Article

The Dynamics of Noble Metal Atom Penetration through Methoxy-Terminated Alkanethiolate Monolayers

Amy V. Walker,*^† Timothy B. Tighe, Orlando M. Cabarcos, Michael D. Reinard, Brendan C. Haynie, Sundararajan Uppili, Nicholas Winograd,* and David L. Allara*; ;

Contribution from the Department of Chemistry, Pennsylvania State University, 184 Materials Research Institute, University Park, Pennsylvania 16802

J. Am. Chem. Soc., 2004, 126 (12), pp 3954–3963

DOI: 10.1021/ja0395792

Publication Date (Web): March 6, 2004

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

†

Present address: Department of Chemistry, Washington University in St. Louis, Campus Box 1134, St. Louis, MO 63130.

nxw@psu.edu; dla3@psu.edu; walker@wustl.edu

Abstract

We have studied the interaction of vapor-deposited Al, Cu, Ag, and Au atoms on a methoxy-terminated self-assembled monolayer (SAM) of HS(CH₂)₁₆OCH₃ on polycrystalline Au{111}. Time-of-flight secondary ion mass spectrometry, infrared reflection spectroscopy, and X-ray photoelectron spectroscopy measurements at increasing coverages of metal show that for Cu and Ag deposition at all coverages the metal atoms continuously partition into competitive pathways: penetration through the SAM to the S/substrate interface and solvation-like interaction with the −OCH₃ terminal groups. Deposited Au atoms, however, undergo only continuous penetration, even at high coverages, leaving the SAM “floating” on the Au surface. These results contrast with earlier investigations of Al deposition on a methyl-terminated SAM where metal atom penetration to the Au/S interface ceases abruptly after a 1:1 Al/Au layer has been attained. These observations are interpreted in terms of a thermally activated penetration mechanism involving dynamic formation of diffusion channels in the SAM via hopping of alkanethiolate−metal (RSM-) moieties across the surface. Using supporting quantum chemical calculations, we rationalized the results in terms of the relative heights of the hopping barriers, RSAl > RSAg, RSCu > RSAu, and the magnitudes of the metal−OCH₃ solvation energies.