Structures of Self-Assembled n-Alkanethiols on Gold by Reflection High-Energy Electron Diffraction

01 June 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


TThe structures of long-chain alkanethiols (C18H37SH) chemisorbed on an Au(111) single crystal were investigated using reflection high-energy electron diffraction (RHEED). The primary (√3x√3)R30° structure observed as a major species in the as-deposited films contains gold adatoms below the sulfur headgroups. Between the small ordered domains with the alkyl chains tilting toward six directions are azimuthally disorderly packed regions, with a similar average tilt of 30.2°. In contrast, a significant reduction in the coverage of gold adatoms is found in the thermally-induced (2√3x3)rect phase. This superlattice is shown to contain a mixture of two sulfur arrangements, both of which exhibit a small S‒S distance, and the pairing of the aliphatic chains. A microscopic picture is then given for the structural transition. These findings demonstrate how the RHEED technique may be used to resolve structures of nanometer-thick thin films with multiple orders at the interfaces.


self-assembled monolayer
superlattice structures
gold adatoms
Structural transitions


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