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Dynamics within alkylsiloxane self-assembled monolayers studied by sensitive dielectric spectroscopy.

Self-assembled monolayers are a ubiquitous laboratory tool and have been the subject of many experimental investigations which have primarily focused on static properties of full coverage monolayers, with the maximum density and ordering possible. In this work, dynamics within low density, planar siloxane self-assembled monolayers are studied utilizing highly sensitive dielectric spectroscopy. Dilute, disordered films were intentionally fabricated in order to study the widest range of possible motions. At low coverage, an interacting relaxation is observed, which has similar dynamics to polyethylene-like glass transitions observed in phase-segregated side-chain polymers, despite the rigidity of the substrate and the constraint of ethyl groups in relatively short chains. As density is increased, a second local relaxation, previously observed in three-dimensional SAMs and associated with rotation within a small segment of the alkyl chain, is also observed.