Fabrication of Asymmetric Molecular Junctions by the Oriented Assembly of Dithiocarbamate Rectifiers

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• 作者：Deqing Gao ; Frank Scholz ; Heinz-Georg Nothofer ; William E. Ford ; Ullrich Scherf ; Jurina M. Wessels ; Akio Yasuda ; Florian von Wrochem
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：April 20, 2011
• 年：2011
• 卷：133
• 期：15
• 页码：5921-5930
• 全文大小：1109K
• 年卷期：v.133,no.15(April 20, 2011)
• ISSN：1520-5126

文摘

The oriented assembly of molecules on metals is a requirement for rectification in planar metal鈭抦olecule鈭抦etal junctions. Here, we demonstrate how the difference in adsorption kinetics between dithiocarbamate and thioacetate anchor groups can be utilized to form oriented assemblies of asymmetric molecules that are bound to Au through the dithiocarbamate moiety. The free thioactate group is then used as a ligand to bind Au nanoparticles and to form the desired metal鈭抦olecule鈭抦etal junction. Besides allowing an asymmetric coupling to the electrodes, the molecules exhibit an asymmetric molecular backbone where the length of the alkyl chains separating the electrodes from a central, para-substituted phenyl ring differs by two methylene units. Throughout the junction fabrication, the layers were characterized by photoelectron spectroscopy, infrared spectroscopy, and scanning tunneling microscopy. Large area junctions using a conducting polymer interlayer between a mercury-drop electrode and the self-assembled monolayer prove the relationship between electrical data and molecular structure.