Strong Substrate–Adsorbate Interactions Direct the Impact of Fluorinated N-Heterocyclic Carbene Monolayers on Au Surface Properties

Abstract

Fluorinated self-assembled monolayers (SAMs) have been utilized in a variety of applications such as transistors and optoelectronic devices. However, in most SAMs the fluorinated groups could not be positioned in high proximity to the surface due to steric effects. This limitation hinders the direct analysis of the impact of the fluorination level on surface properties. Herein, fluorinated aromatic N-heterocyclic carbenes (NHCs), with 1−5 fluorine atoms, were self-assembled on a gold substrate. These NHCs enabled the positioning of fluorinated groups in high proximity to the metal surface to identify the influence of the fluorination level on surface properties. Experimental measurements and theoretical calculations identified that all fluorinated NHCs formed SAMs and adopted a flat-lying adsorption configuration while anchored to the metal surface via Au adatom. A higher fluorination level induced a stronger interaction of the fluorinated side groups with the Au surface. The stronger interaction and surface proximity of the fluorinated side groups deteriorated the overall binding energy of the NHC due to the lessoptimized adsorption geometry of the carbene carbon. Ultraviolet photoelectron spectroscopy measurements revealed that fluorinated NHC monolayers lowered the surface work function by up to 1 eV and induced an increase of 15−20°in the water contact angle. The impact on surface properties did not vary according to the fluorination level of NHCs, and similar values were measured for NHC with 1−5 fluorine atoms. It is therefore identified that dominant adsorbate−substrate interactions between the fluorinated side groups and the Au surface quenched the distinct impact of the fluorination level on surface functionality.