Self-assembled alkanethiol monolayers on gold surfaces: resolving the complex structure at the interface by STM

The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the s...

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Published inPhysical chemistry chemical physics : PCCP Vol. 16; no. 36; pp. 1974 - 199
Main Authors Guo, Quanmin, Li, Fangsen
Format Journal Article
LanguageEnglish
Published England 01.01.2014
Subjects
Alkanes
Chains
Gold
Molecular structure
Monolayers
Phase transformations
Sulfur
Surface chemistry
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Abstract The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n -propanethiol to n -butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./ c (4 × 2) phase for long chain molecular monolayers. New insights into the classical system of self-assembled alkanethiol monolayers on Au(111).
AbstractList The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n -propanethiol to n -butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./ c (4 × 2) phase for long chain molecular monolayers. New insights into the classical system of self-assembled alkanethiol monolayers on Au(111).
The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is viathe formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 2[radic]3)-rect./c(4 2) phase for long chain molecular monolayers.
The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.
The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a molecular layer is via the formation of self-assembled monolayers (SAMs). The molecules that form SAMs have a functionality which binds to the surface and the adsorption is self-regulated to terminate at exactly one single molecular layer. The very first example, which has become the most widely studied system, of SAMs on metal surfaces consists of chemisorbed alkylthiolate on gold. Despite the simplicity in the preparation of alkanethiol SAMs and the seemingly straightforward structure of such SAMs, the detailed bonding between the sulfur head group and gold is still subject to debate. Experimental and theoretical effort in the last six years has led to a much improved understanding of this classical system of SAMs. In this review, we will highlight the most recent progress in the study of the interfacial structure of alkanethiol SAMs on gold. We focus on the important phenomenon of phase transition that occurs from n-propanethiol to n-butanethiol, and propose a unified structural model to explain how the (3 × 4) phase for short chain alkanethiol monolayers (methyl-, ethyl- and propylthiolate monolayers) changes into the (3 × 2√3)-rect./c(4 × 2) phase for long chain molecular monolayers.
Author Li, Fangsen
Guo, Quanmin
AuthorAffiliation University of Birmingham
Tsinghua University
School of Physics and Astronomy
Department of Physics
AuthorAffiliation_xml – name: Department of Physics
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  surname: Guo
  fullname: Guo, Quanmin
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BackLink https://www.ncbi.nlm.nih.gov/pubmed/24777119$$D View this record in MEDLINE/PubMed
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Notes Quanmin Guo is a Senior Lecturer at the School of Physics and Astronomy, University of Birmingham. His research interest is in the area of two-dimensional nano-materials, in particular, nanoscale structures grown on solid substrates. His current work focuses on the characterization of molecular self-assembly using scanning probe based techniques. He obtained his PhD from the University of Lancaster in 1989, and worked as a research associate in the Surface Science Research Centre at the University of Liverpool before joining the University of Birmingham in 1998.
Fangsen Li received his PhD from the School of Materials Science and Engineering of the Northwestern Polytechnical University in Xi'an, China in 2011. He visited the Nanoscale Physics Research Laboratory (NPRL) of the University of Birmingham as a joint doctoral student in 2008-2010, working on the characterization of alkanethiol SAMs with STM. He moved to his present position, postdoctoral researcher in Tsinghua University in Beijing, China in 2012. His current research is in the area of structural and electronic properties of ultra thin films and heterostructures.
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Snippet The surface properties of metals and metal oxides can be modified by adding a single layer of organic molecules. A most popular route for depositing such a...
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StartPage 1974
SubjectTerms Alkanes
Chains
Gold
Molecular structure
Monolayers
Phase transformations
Sulfur
Surface chemistry
Title Self-assembled alkanethiol monolayers on gold surfaces: resolving the complex structure at the interface by STM
URI https://www.ncbi.nlm.nih.gov/pubmed/24777119
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