We have studied the structure and growth process of hexanethiolate self-assembled monolayers (SAMs) on Cu(100) by means of scanning tunneling microscopy (STM) and X-ray absorption fine structure (XAFS) spectroscopy. At saturated coverage, the thiolates are assembled into a c(2 × 6) structure with zigzag chains along the close-packed Cu rows. The sulfur atom of the thiolate occupies the 4-fold hollow site of the unreconstructed Cu(100) surface with a nearest-neighbor S-S distance of 3.6 Å. Such sulfur adsorption results in a large lattice mismatch between the S/Cu layer and the alkyl chain layer, since the interchain distance of the alkyl group is ca. 4.5 Å. However, it is reconciled by the internal degree of freedom for the S-C bond which bridges the two layers, as is confirmed by the geometrical optimization based on molecular force-field calculations. The SAM film formation is well-described by a two-step process; in the first step, a full-coverage monolayer is rapidly formed, which is characterized by a highly oriented but two-dimensionally disordered structure, followed by a much slower evolution to the c(2 × 6) structure with surface diffusion of the thiolate.
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