Direct Covalent Grafting of Conjugated Molecules onto Si, GaAs, and Pd Surfaces from Aryldiazonium Salts

Michael P. Stewart, Francisco Maya, Dmitry V. Kosynkin, Shawn M. Dirk, Joshua J. Stapleton, Christine L. McGuiness, David L. Allara,* and James M. Tour*
Contribution from the Departments of Chemistry and Mechanical Engineering and Materials Science, and Center for Nanoscale Science and Technology, MS-222, Rice University, Houston, Texas 77005, and Department of Chemistry and Department of Materials Science, Pennsylvania State University, University Park, Pennsylvania 16802
J. Am. Chem. Soc., 2004, 126 (1), pp 370–378
DOI: 10.1021/ja0383120
Publication Date (Web): December 16, 2003
Copyright © 2004 American Chemical Society

Abstract

Abstract Image

Using aryldiazonium salts that are air-stable and easily synthesized, we describe here a one-step, room-temperature route to direct covalent bonds between π-conjugated organic molecules on three material surfaces:  Si, GaAs, and Pd. The Si can be in the form of single crystal Si including heavily doped p-type Si, intrinsic Si, heavily doped n-type Si, on Si(111) and Si(100), and on n-type polycrystalline Si. The formation of the aryl−metal or aryl−semiconductor bond attachments was confirmed by corroborating evidence from ellipsometry, reflectance FTIR, XPS, cyclic voltammetry, and AFM analyses of the surface-grafted monolayers. A data-encompassing explanation for the mechanism suggests a diazonium activation by reduction at the open circuit potential, with aryl radical secondary products bonding to the surface. The synthetic details are included for preparing the surface-grafted monolayers and the precursor diazonium salts. This spontaneous diazonium activation reaction offers an attractive route to highly passivating, robust monolayers and multilayers on many surfaces that allow for strong bonds between carbon and surface atoms with molecular species that are near perpendicular to the surface.

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History

  • Published In Issue January 14, 2004
  • Received September 3, 2003

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