N-Heterocyclic Carbenes - the Design Concept for Densely Packed and Thermally Ultra-Stable Aromatic Self-Assembled Monolayers

Abstract

Self-assembled monolayers (SAMs) of N-heterocyclic carbenes (NHCs) on metal substrates are currently one of the most promising systems in context of molecular-scale engineering of surfaces and interfaces, crucial for numerous applications. Interest in NHC SAMs is mainly driven by their assumingly higher thermal stability compared to thiolate SAMs most broadly used at the moment. Most of the NHC SAMs utilize imidazolium as an anchoring group for linking molecules to the metal substrate via carbene C atom. It is well established in the literature that standing up and stable NHC SAMs are built only when using bulky side groups attached to nitrogen heteroatoms in imidazolium moiety, which, however, leads to monolayers exhibiting much lower packing density compared to thiolate SAMs. Here, by combined X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and temperature-programmed secondary ion mass spectrometry analysis, we demonstrate that using NHCs with small methyl side groups in combination with simple solution-based preparation leads to the formation of aromatic monolayers exhibiting at least double surface density, upright molecular orientation, and ultra-high thermal stability compared to the NHC SAMs reported before. These parameters are crucial for most applications, including, in particular, molecular and organic electronics, where aromatic SAMs serve either as a passive element for electrode engineering or as an active part of organic field effect transistors and novel molecular electronics devices.

Correction to N-Heterocyclic Carbenes for the Self-Assembly of Thin and Highly Insulating Monolayers with High Quality and Stability

“…To address the packing density and orientation of BIM molecules on the Au surface, we have conducted additional XPS and NEXAFS studies, respectively, which confirm the formation of high-density structures by upright-oriented molecules. This data, as a part of an extended analysis for the series of NHC SAMs formed by molecules with short methyl side groups, can be found elsewhere …”

“…The correction affects only the STM data and directly related detail conclusions, i.e., the unit cell description and estimation of defects concentration in the monolayer. The general conclusions of high packing density and upright molecular orientation of the BIM/Au monolayer, which were originally based mainly on the STM data, are confirmed now by using other techniques as shown in ref . All other conclusions presented in our paper remain unaffected by the current correction.…”