The Self-Assembly Mechanism of Alkanethiols on Au(111)

Poirier, G. E.; Pylant, E. D.

doi:10.1126/science.272.5265.1145

Cited by 792 publications

(885 citation statements)

References 23 publications

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“…As discussed above, the coordinate bond could actually form between the -SH group and gold surface in the initial stage, followed by the dissociation of S-H bond that results in a thiyl radical, which would finally form a gold-thiolate covalent bond at the gold-sulfur interface [45][46][47][48][49][50][51][54][55][56][57][58] . These findings indicate that the formation of Au-S covalent bonds needs a certain time to complete.…”

Section: Resultsmentioning

confidence: 99%

“…The adsorption of thiol onto gold surface starts with physisorption, during which the H atom favourably remains on the S atom, followed by a chemisorption including the breaking of S-H bond and the formation of a Au-S bond as a result of the deprotonation of thiols and formation of thiyl radicals [45][46][47][48][49][50][51] . The existence of the dissociated hydrogen could affect the pH value of the microenvironment around the Au-S binding sites.…”

Section: Resultsmentioning

confidence: 99%

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Quantifying thiol–gold interactions towards the efficient strength control

et al. 2014

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The strength of the thiol-gold interactions provides the basis to fabricate robust self-assembled monolayers for diverse applications. Investigation on the stability of thiol-gold interactions has thus become a hot topic. Here we use atomic force microscopy to quantify the stability of individual thiol-gold contacts formed both by isolated single thiols and in self-assembled monolayers on gold surface. Our results show that the oxidized gold surface can enhance greatly the stability of gold-thiol contacts. In addition, the shift of binding modes from a coordinate bond to a covalent bond with the change in environmental pH and interaction time has been observed experimentally. Furthermore, isolated thiol-gold contact is found to be more stable than that in self-assembled monolayers. Our findings revealed mechanisms to control the strength of thiol-gold contacts and will help guide the design of thiol-gold contacts for a variety of practical applications.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Quantifying thiol–gold interactions towards the efficient strength control

et al. 2014

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“…Both the formation dynamics including several intermediate phases and the steady-state SAM structures have been characterized by UHV-STM. [107][108][109][110][111] The advantages of such studies are to offer a fundamental understanding of the formation mechanism as well as the detailed surface structures of the SAMs. However, a broad range of SAMs have been prepared more practically using wet methods.…”

Section: Assembly Environmentsmentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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Self-assembled organization of functional molecules on solid surfaces has developed into a powerful and sophisticated tool for surface chemistry and nanotechnology. A number of reviews on the topic have been available since the mid 1990s. This perspective article aims to focus on recent development in the investigations of electronic structures and assembling dynamics of electrochemically controlled self-assembled monolayers (SAMs) of thiol containing molecules on gold surfaces. A brief introduction is first given and particularly illustrated by a Table summarizing the molecules studied, the surface lattice structures and the experimental operating conditions. This is followed by discussion of two major high-resolution experimental methods, scanning tunnelling microscopy (STM) and single-crystal electrochemistry. In Section 3, we briefly address choice of supporting electrolytes and substrate surfaces, and their effects on the SAM structures. Section 4 constitutes the major body of the article by offering some details of recent studies for the selected cases, including in situ monitoring of assembling dynamics, molecular electronic structures, and the key external factors determining the SAM packing. In Section 5, we give examples of what can be offered by theoretical computations for the detailed understanding of the SAM electronic structures revealed by STM images. A brief summary of the current applications of SAMs in wiring metalloproteins, design and fabrication of sensors, and single-molecule electronics is described in Section 6. In the final two sections (7 and 8), we discuss the current status in understanding of electronic structures and properties of SAMs in electrochemical environments and what could be expected for future perspectives.

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confidence: 99%

“…Vacuum deposition of thiols allows the study of low coverages, and a large variety of different alkanethiols patterns have been reported. [9][10][11][12] To the best knowledge of the authors, low coverages of arenethiols have not been addressed so far, although arenethiols have much larger potential for electronic applications than alkanethiols. This study uses thiophenol (TP) and its p-bromo-(BTP), p-chloro-(CTP), p-fluoro-(FTP), and pentafluoro-substituted (5FTP) analogues as model compounds for arenethiol film formation and explores the impact of a slight variation of arenethiol size and substituent electronegativity (EN) on the films' structural properties.…”

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confidence: 99%

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

et al. 2004

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Thiol films on noble metal surfaces attract considerable interest due to their ability of facile self-assembly from the solution phase. 1 Films of only monomolecular thickness can modify the electronic, physical, and chemical properties of the underlying substrate dramatically. This offers powerful opportunities for fundamental studies of electron transport, 2 single-molecule devices (e.g., tunneling diodes 3 or transistor 4 ), control of surface wettability, 5 etc. The formation of thiol films is driven predominantly by strong substrate-sulfur interactions. At saturation coverage, the result is a layer of molecules that stand close to upright on the surface. For alkanethiols on Au(111), ( 3 x 3)R30°and related superlattices were inferred. [6][7][8] In a solution environment, it is difficult to follow the initial stages of thiol chemisorption because of their high surface mobility prior to formation of a dense film and the presence of the surrounding solution. Vacuum deposition of thiols allows the study of low coverages, and a large variety of different alkanethiols patterns have been reported. [9][10][11][12] To the best knowledge of the authors, low coverages of arenethiols have not been addressed so far, although arenethiols have much larger potential for electronic applications than alkanethiols. This study uses thiophenol (TP) and, and pentafluoro-substituted (5FTP) analogues as model compounds for arenethiol film formation and explores the impact of a slight variation of arenethiol size and substituent electronegativity (EN) on the films' structural properties. We studied a broad range of coverages and found the most dramatic effects at incomplete films, where the molecules aggregate into isolated islands that are separated by empty terraces.We used two home-built STM systems that were operated in UHV (<10 -10 Torr) at cryogenic temperatures (15 or 81 K). Multiple cryopanels enclosed the STMs in order to minimize drift and sample contamination. We used a Cu(111) single crystal as a substrate. Sample preparation involved cycles of sputtering (Ar, 1.5 keV) and annealing (600 K). All arenethiol coverages were prepared by backfilling the chamber to a pressure of ∼10 -9 Torr and (if necessary, multiple cycles of) sample exposure for ∼15 s.We observed spontaneous formation of the superlattices in Figure 1 at 81K, which suggests that they may form transiently during the deposition of larger coverages. Figure 1a,b shows STM images of isolated CTP and TP molecules at 15 K after hydrogen abstraction. The molecules adsorb flat on the surface, and their image has a depression that we associate with the position of the thiol group. Using lateral manipulation 13 and coadsorption of CO for registry, 14 we find that both the S and the halogen atoms occupy Cu(111) hollow sites. The overall shape of FTP, 5FTP, and BTP is similar to Figure 1a,b and their size scales with the dimension of the substituent(s). Figure 1c-f shows a clean Cu(111) surface and islands of the parasubstituted molecules. Fourier transformation (FT) ...

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The Self-Assembly Mechanism of Alkanethiols on Au(111)

Cited by 792 publications

References 23 publications

Quantifying thiol–gold interactions towards the efficient strength control

Quantifying thiol–gold interactions towards the efficient strength control

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Effect of Halo Substitution on the Geometry of Arenethiol Films on Cu(111)

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