The purpose of research on metals (M) deposited onto self‐assembled monolayers (SAMs) is to understand the interactions between the metal and eventually metal oxide overlayers on well‐ordered organic surfaces. Applications of M/SAM and inorganic/SAM research results to the understanding of real inorganic/organic interfaces in vacuum and under environmental conditions can potentially play a key role in the development of advanced devices with stable interfacial properties. The results of M/SAM studies to date are reviewed, M/SAM combinations ranked according to reactivity and penetration, and specific examples of reactive interfaces (Cu/COOH, and Cr/COOH) and nonreactive interfaces with penetration (Ag/COOH) are used to illustrate the extremes.

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