The electron dynamics in alkanethiolate self-assembled monolayers (Cn-SAMs; n = 6-18, where n is the number of alkyl carbons) formed on Au(111) surfaces has been investigated by time- and angle-resolved two-photon photoemission spectroscopy. The time evolution of photoexcited electrons flowing down into image potential states (IPSs) formed on standing-up structure of SAMs is resolved two-dimensionally; the electron lifetime in the IPS increases with chain length, from sub-ps to 100 ps. The chain length dependence of the IPS lifetime is particularly marked at shorter chain lengths of n = 6-10, whereas it becomes milder at chain lengths above n = 10, whose alkyl layer thickness is ≈10 Å. This thickness dependence can be explained by two competitive channels for the decay of IPS electrons: one is electronic coupling of IPS with unoccupied bulk Au states and an interfacial state localized at the Au-S linkage, and the other is IPS electron decay to the Au substrate through a tunneling barrier of insulating alkyl chains. The former is most influential at shorter chain lengths, while the latter is solely dominant at longer chain lengths. In addition, the photon energy dependence of the IPS intensity revealed that electron injection into the IPS is mediated effectively by an electron excitation into interfacial resonance formed in the alkyl layer.
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