Self-assembly of methanethiol on the reconstructed Au(111) surface

Nenchev, Georgi; Diaconescu, Bogdan; Hagelberg, Frank; Pohl, Karsten

doi:10.1103/physrevb.80.081401

Cited by 37 publications

(50 citation statements)

References 27 publications

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“…While a very recent DFT study stated that refilling the vacancies would be energetically favorable, [128] STM results further suggest that also the ad-atoms diffuse and coalesce into gold islands of mono-atomic height. [129] Importantly, this latter finding points toward the fact that the ad-atoms do not actively participate in the sulfur-gold bonding after all and, thus, that the sulfur-pair/ad-atom structural motif might occur only during the initial stages of SAM formation, but maybe no longer plays a dominant role in a completed and densely packed SAM.…”

Section: Notes On the Atomistic Structure Of The Thiol/gold Interfacementioning

confidence: 95%

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

2010

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The modification of electrode surfaces by depositing self-assembled monolayers (SAMs) provides the possibility for controlled adjustment of various key parameters in organic and molecular electronic devices. Most important among them are the work function of the electrode and the relative alignment of its Fermi level with the conducting states in the SAM itself and with those in a subsequently deposited organic semiconductor. For the efficient application of such interface modifications it is crucial to reach a proper understanding of the relation between the chemical structure of a molecule, its molecular electronic characteristics, and the properties of the SAM formed by such molecules. Over the past years, quantum-mechanical calculations have proven to be a valuable tool for reaching a fundamental understanding of the relevant structure-property relations. Here, we provide a review over the field and report on recent progress in the modeling of the interfacial electronic properties of pi-conjugated SAMs. In addition to the insight that can be gained from simple electrostatic considerations, we focus on the quantum-mechanical description of the roles played by substituents, molecular backbones, chemical anchoring groups, and the packing density of molecules on the surface. Furthermore, we explicitly address the energy-level alignment at the interface between a prototypical organic semiconductor and a SAM-covered metal electrode and describe an approach suitable for extending the metallic character of the substrate onto the monolayer.

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Section: Notes On the Atomistic Structure Of The Thiol/gold Interfacementioning

confidence: 95%

Modeling the Electronic Properties of π‐Conjugated Self‐Assembled Monolayers

2010

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“…c After the extra ≈4.5 % surface gold atoms are removed, the herringbones disappear completely and their spacing is essentially infinite; this phenomenon is generally observed for species with higher adsorption energies 1d. 5a, b, 18c, 35 Herein, we use the spacing of the herringbone reconstruction as a sensitive measure of the interaction strength between gold and the four aforementioned molecules. The herringbone separation was measured at various coverage and temperature treatments with the premise that a larger herringbone separation at similar conditions is indicative of a stronger interaction of the molecule with the surface.…”

Section: Resultsmentioning

confidence: 99%

Effect of Head‐Group Chemistry on Surface‐Mediated Molecular Self‐Assembly

Jewell

Kyran

Rabinovich

et al. 2012

Chemistry A European J

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Surface molecular self-assembly is a fast advancing field with broad applications in sensing, patterning, device assembly, and biochemical applications. A vast number of practical systems utilize alkane thiols supported on gold surfaces. Whereas a strong Au-S bond facilitates robust self-assembly, the interaction is so strong that the surface is reconstructed, leaving etch pits that render the monolayers susceptible to degradation. By using different head group elements to adcust the molecule-surface interaction, a vast array of new systems with novel properties may be formed. In this paper we use a carefully chosen set of molecules to make a direct comparison of the self-assembly of thioether, selenoether, and phosphine species on Au(111). Using the herringbone reconstruction of gold as a sensitive readout of molecule-surface interaction strength, we correlate head-group chemistry with monolayer (ML) properties. It is demonstrated that the hard/soft rules of inorganic chemistry can be used to rationalize the observed trend of molecular interaction strengths with the soft gold surface, that is, P>Se>S. We find that the structure of the monolayers can be explained by the geometry of the molecules in terms of dipolar, quadrupolar, or van der Waals interactions between neighboring species driving the assembly of distinct ordered arrays. As this study directly compares one element with another in simple systems, it may serve as a guide for the design of self-assembled monolayers with novel structures and properties.

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“…The native herringbone structure of gold is lifted as Au atoms are ejected from the surface layer, and this process often occurs in conjunction with molecular adsorption [23,64,66,67]. If adsorbed species are deposited quickly, the ejected Au adatoms can be trapped near the ejection point [65,68].…”

Section: Surface Interaction: Lifting Gold's Herringbone Reconstructionmentioning

confidence: 99%

“…For example, the most common type of SAM involves thiol species (HSR) and utilizes a strong sulfurmetal interaction to form the layers [21][22][23][24][25]. Thiols can be functionalized with groups that are polar, aromatic, etc.…”

Section: Introductionmentioning

confidence: 99%