Optical Characterization of Thiolate Self-Assembled Monolayers on Au(111)

We have investigated the optical response of thiolate self-assembled monolayers (SAMs) deposited from the liquid phase on well characterized, (111)-textured gold films based on the use of in situ and ex situ optical spectroscopic ellipsometry. We considered SAMs formed by several molecules with thiol functionality, focusing on the octadecanethiol (C18) SAM model system. We were able to show the tiny spectroscopic variations induced by the monolayer thick films with great reproducibility and high signal-to-noise ratio. We identified spectral features related to the alkyl chain and to the S−Au interface, providing a reliable spectral “fingerprint” of the formation of densely packed thiolate layers. By comparing data with simulations based on several effective models developed within the framework of Fresnel approach, we identified the main optical features related to the thiolate interface and in particular an absorption band whose spectral weight increases regularly from 500 nm toward the IR limit. We also obtained reliable estimations of the SAM thickness. The interface absorption properties have been tentatively assigned to a modification of the nearly free electron behavior, related to nanoscale morphological modifications following the formation of Au−thiolate moieties.