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Published online by Cambridge University Press: 21 February 2011
The adsorption kinetics of self-assembling n-alkyl thiol films on poly cry stalline gold substrates was studied in situ by optical second harmonic generation (SHG). The relation between the SHG signal change and the thiol coverage was established by comparison with ex situ X-ray photoelectron spectroscopy measurements. We find that the temporal dependence of the adsorption is well described by Langmuir adsorption kinetics. The source of the SHG signal is found to be linearly related to the nonlinear susceptibility of the adsorbate-substrate interaction. Experiments with chain lengths ranging from 1 to 22 showed, that the saturation coverage for thiols longer than hexanethiol is equal.