We show that the electrode/molecule chemical bond does not change the tunneling barrier for charge transport through alkyl chain monolayers sandwiched between Si and Hg electrodes. This observation can be understood if the interfacial bond mainly governs the monolayer's structure, while the electronic states due to molecule-electrode bonding do not contribute significantly to tunneling. Yet, the nature of the bond affects the Schottky barrier inside the semiconductor due to changes in the interface dipole.
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