Rapid Self-Assembly of Alkanethiol Monolayers on Sputter-Grown Au(111)

Abstract

Atomically flat, sputter-grown Au(111) films allowed well-ordered alkanethiol (exemplified by octanethiol) monolayers to be self-assembled from solution markedly faster and in larger domain sizes than previously reported. An X-ray photoelectron spectroscopy analysis showed that complete monolayer coverage was reached by 0.2−60 min of incubation in 0.1−0.001 mM ethanolic solution at room temperature (∼17 °C), with single-step (0.1 and 0.01 mM) or two-step (0.001 mM) adsorption kinetics. Increasing the temperature to 35 °C was enough to cause a single-step, diffusion-controlled adsorption also from the 0.001 mM solution, yielding the full monolayer coverage in approximately 10 min. Scanning tunneling microscopy (STM) imaging proved that well-ordered islands, with the (√3 × √3)R30° structure more-or-less strongly modulated by the c(4 × 2) superlattice, begin to form at 0.6−0.7 monolayer coverage most likely by homogeneous nucleation and grow rapidly thereafter. This kinetics of ordering requiring the considerably high threshold coverage for the nucleation, but allowing the fast growth of the nuclei was independently confirmed by the infrared reflection absorption spectroscopy. A typical c(4 × 2) domain size at the saturation coverage was estimated to be no less than 10−15 nm, and the structural identity often seemed not to be disrupted even across the etch pits. This superior structural order is reflected on the highest level of molecular resolution achieved by the in-air STM imaging. The expected registry of the (√3 × √3)R30° or c(4 × 2) lattice with that of Au(111) was also confirmed. On Au films that were also sputter-grown but no longer atomically flat, we observed at least by 1 order of magnitude slower self-assembly.

Revisited BIA-MS combination: Entire “on-a-chip” processing leading to the proteins identification at low femtomole to sub-femtomole levels

“…This was confirmed using contact angle measurements as summarized in Fig. 1B, the average angle formed by small water drops onto the SAM reached 107 ± 2 • , which is close to the value expected for such a substrate (Kawasaki et al, 2000). Hydrophobicity is the driving force, which allows the adsorption of a large number of biological compounds (proteins, nucleic acids, lipids, etc.).…”

Surface Stress, Kinetics, and Structure of Alkanethiol Self-Assembled Monolayers

“…On small-grained gold, alkanethiol domains of the lying-down phase form, but their growth is inhibited in sorne fashion, so that a full conversion into the standing-up phase does not occur. We note that the average size of atomically flat areas available for formation of ordered domains (composing the full SAM) on the small-grained gold is of the same order of magnitude as typical domain sizes (-10 nm) that are observed for well-ordered SAMs [115,144]. Sorne STM studies suggest that it is energetically favorable for nucleation of the standing-up phase to occur at domain boundaries of the lying-down phase, through the so-called disordered phase.…”

Parameters Important in Fabricating Enzyme Electrodes Using Self-Assembled Monolayers of Alkanethiols

“…There has been considerable research into both the time required for SAM formation 44,45 and the optimal conditions for activating carboxylic acid terminated SAMs with EDC and NHS. [46][47][48][49] Therefore, the conditions of SAM formation and activation were not investigated further in this study.…”