Molecular self-assembly guided by surface reconstruction: CH3SH monolayer on the Au(111) surface

Maksymovych, Peter; Dougherty, Daniel B.

doi:10.1016/j.susc.2008.03.047

Cited by 20 publications

(16 citation statements)

References 26 publications

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“…Thus, the small structural differences between the different orientations produced by the anisotropic compression of the gold surface make that, for a given direction of the surface reconstruction, only two domains are observed (domains I and II in Figure 21b). A similar influence of the gold surface reconstruction on the orientation of other molecular systems (methanethiol,147 bipyridine148 on Au(111) has been previously reported.…”

Section: The Substrate Is Strongly Modified By the Molecular Adsorsupporting

confidence: 80%

1,1′‐Binaphthyl‐2‐methylpyridinium‐Based Peroxophosphotungstate Salts: Synthesis, Characterization, and Their Use as Oxidation Catalysts

Jahier¹,

Felpin²,

Méliet³

et al. 2009

Eur J Inorg Chem

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Self‐assembly, the process by which objects initially distributed at random arrange into well‐defined patterns exclusively due to their local mutual interactions without external intervention, is generally accepted to be the most promising method for large‐scale fabrication of functional nanostructures. In particular, the ordering of molecular building‐blocks deposited at solid surfaces is relevant for the performance of many organic electronic and optoelectronic devices, such as organic field‐effect transistors (OFETs), organic light‐emitting diodes (OLEDs) or photovoltaic solar cells. However, the fundamental knowledge on the nature and strength of the intermolecular and molecule‐substrate interactions that govern the ordering of molecular adsorbates is, in many cases, rather scarce. In most cases, the structure and morphology of the organic‐metal interface is not known and it is just assumed to be the same as in the bulk, thereby implicitly neglecting the role of the surface on the assembly. However, this approximation is usually not correct, and the evidence gathered over the last decades points towards an active role of the surface in the assembly, leading to self‐assembled structures that only in a few occasions can be understood by considering just intermolecular interactions in solid or gas phases. In this work we review several examples from our recent research demonstrating the apparently endless variety of ways in which the surface might affect the assembly of organic adsorbates.

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Section: The Substrate Is Strongly Modified By the Molecular Adsorsupporting

confidence: 80%

1,1′‐Binaphthyl‐2‐methylpyridinium‐Based Peroxophosphotungstate Salts: Synthesis, Characterization, and Their Use as Oxidation Catalysts

Jahier¹,

Felpin²,

Méliet³

et al. 2009

Eur J Inorg Chem

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“…However, our results strongly suggest that the spontaneous change in the adsorption geometry is driven by intermolecular interactions. The bonding geometry is different from the one proposed earlier 16 as the molecular rows are bonded iteratively to shifted-bridge and shifted-top sites in zigzag orientation, as shown in Figs. 2͑d͒ and 2͑e͒.…”

mentioning

confidence: 60%

“…The dimerization mechanism and the bonding geometry are still extensively debated. [7][8][9][10][11][12] For the adsorption of the simplest thiol molecule, CH 3 SH on Au͑111͒ only very recent observational 9,[13][14][15][16] and theoretical 17,18 results are available. While desorption data seem still inconclusive, 9,13 initial scanning tunneling microscopy ͑STM͒ studies show the absence of self-assembly, 13 on-top adsorption at submonolayer ͑ML͒ exposures 14 without affecting the substrate reconstruction.…”

mentioning

confidence: 99%

“…However, a very recent STM study revealed a continuous ordered structure. 16 At the same time a density-functional theory ͑DFT͒ calculation 18 proposed the possibility of dimerization of the nondissociated CH 3 SH adsorbate on unreconstructed Au͑111͒, driven by substratemediated charge exchange rather than van der Waals forces. In this Rapid Communication we show that CH 3 SH not only spontaneously dimerizes on reconstructed Au͑111͒ but also forms two stable continuous self-assembled structures.…”

mentioning

confidence: 99%

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

et al. 2009

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We present a combined experimental and theoretical study of molecular methanethiol ͑CH 3 SH͒ adsorption on the reconstructed Au͑111͒ surface in the temperature range between 90 and 300 K in UHV. We find that the simplest thiol molecules form two stable self-assembled monolayer ͑SAM͒ structures that are created by distinct processes. Below 120 K, a solid rectangular phase, preserving the herringbone reconstruction, emerges from individual chains of spontaneously formed dimers. At higher adsorption temperatures below 170 K, a close-packed phase forms via dissociative CH 3 SH adsorption and the formation of Au adatoms that are not incorporated into the SAM. We show that the combination of a strong substrate-mediated interaction with nondissociative dimerization and temperature activated removal of the Au͑111͒ reconstruction drives the largescale assembly of molecular CH 3 SH into two distinct phases.

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“…[88][89][90] In contrast, the term ''thiolate'' is commonly used to indicate the molecular species present at the surface at room temperature, reflecting the fact that, there, the SÀH bonds are cleaved. [91,92] Note that, as opposed to the -S termination mentioned above, ''thiolate'' actually refers to an -S À species and will in the following be used to denote molecules bonded via a sulfur group even, as will be shown below, when there is actually little evidence for pronounced negative charging of the sulfur on the surface.…”

Section: Dissociative Adsorption Of Thiols On Goldmentioning

confidence: 99%

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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Molecular self-assembly guided by surface reconstruction: CH3SH monolayer on the Au(111) surface

Cited by 20 publications

References 26 publications

1,1′‐Binaphthyl‐2‐methylpyridinium‐Based Peroxophosphotungstate Salts: Synthesis, Characterization, and Their Use as Oxidation Catalysts

1,1′‐Binaphthyl‐2‐methylpyridinium‐Based Peroxophosphotungstate Salts: Synthesis, Characterization, and Their Use as Oxidation Catalysts

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

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

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