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Nano Research 2010, 3(7): 459-471 https://doi.org/10.1007/s12274-010-0005-9
Research Article | Open Access | Issue | Published: 01 June 2010

Interplay of Adsorbate-Adsorbate and Adsorbate-Substrate Interactions in Self-Assembled Molecular Surface Nanostructures

Show Author's Information Joachim Schnadt1,2( ),  Wei Xu1,3,  Ronnie T. Vang1,  Jan Knudsen1,  Zheshen Li4,  Erik Lægsgaard1,  Flemming Besenbacher1
Interdisciplinary Nanoscience Center, iNANO, and Department of Physics and Astronomy Aarhus University, Building 1521Ny Munkegade 8000 Aarhus C Denmark
Division of Synchrotron Radiation Research Department of Physics, Lund University Box 118, 221 00 Lund Sweden
Shanghai Key Laboratory for Metallic Functional Materials, Key Laboratory for Advanced Civil Engineering Materials (Ministry of Education) College of Materials Science and Engineering, Tongji University, 1239 Si Ping RoadShanghai 200092 China
Institute for Storage Ring Facilities Aarhus University, Building 1525Ny Munkegade 8000 Aarhus C Denmark
Keywords:
hydrogen bonding, X-ray photoelectron spectroscopy, scanning tunnelling microscopy, Molecular self-assembly
Cite this article:
Schnadt J, Xu W, Vang RT, et al. Interplay of Adsorbate-Adsorbate and Adsorbate-Substrate Interactions in Self-Assembled Molecular Surface Nanostructures. Nano Research, 2010, 3(7): 459-471. https://doi.org/10.1007/s12274-010-0005-9
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Abstract Full text About this article

The adsorption of 2, 6-naphthalenedicarboxylic acid (NDCA) molecules on the Ag(110), Cu(110), and Ag(111) surfaces at room temperature has been studied by means of scanning tunnelling microscopy (STM). Further supporting results were obtained using X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS). On the Ag(110) support, which had an average terrace width of only 15 nm, the NDCA molecules form extended one-dimensional (1-D) assemblies, which are oriented perpendicular to the step edges and have lengths of several hundred nanometres. This shows that the assemblies have a large tolerance to monatomic surface steps on the Ag(110) surface. The observed behaviour is explained in terms of strong intermolecular hydrogen bonding and a strong surface-mediated directionality, assisted by a sufficient degree of molecular backbone flexibility. In contrast, the same kind of step-edge crossing is not observed when the molecules are adsorbed on the isotropic Ag(111) or more reactive Cu(110) surfaces. On Ag(111), similar 1-D assemblies are formed to those on Ag(110), but they are oriented along the step edges. On Cu(110), the carboxylic groups of NDCA are deprotonated and form covalent bonds to the surface, a situation which is also achieved on Ag(110) by annealing to 200 ℃. These results show that the formation of particular self-assembled molecular nanostructures depends significantly on a subtle balance between the adsorbate-adsorbate and adsorbate-substrate interactions and that kinetic factors play an important role.


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Interplay of Adsorbate-Adsorbate and Adsorbate-Substrate Interactions in Self-Assembled Molecular Surface Nanostructures

Show Author's information Joachim Schnadt1,2( ), Wei Xu1,3, Ronnie T. Vang1, Jan Knudsen1, Zheshen Li4, Erik Lægsgaard1, Flemming Besenbacher1
Interdisciplinary Nanoscience Center, iNANO, and Department of Physics and Astronomy Aarhus University, Building 1521Ny Munkegade 8000 Aarhus C Denmark
Division of Synchrotron Radiation Research Department of Physics, Lund University Box 118, 221 00 Lund Sweden
Shanghai Key Laboratory for Metallic Functional Materials, Key Laboratory for Advanced Civil Engineering Materials (Ministry of Education) College of Materials Science and Engineering, Tongji University, 1239 Si Ping RoadShanghai 200092 China
Institute for Storage Ring Facilities Aarhus University, Building 1525Ny Munkegade 8000 Aarhus C Denmark

Abstract

The adsorption of 2, 6-naphthalenedicarboxylic acid (NDCA) molecules on the Ag(110), Cu(110), and Ag(111) surfaces at room temperature has been studied by means of scanning tunnelling microscopy (STM). Further supporting results were obtained using X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption spectroscopy (XAS). On the Ag(110) support, which had an average terrace width of only 15 nm, the NDCA molecules form extended one-dimensional (1-D) assemblies, which are oriented perpendicular to the step edges and have lengths of several hundred nanometres. This shows that the assemblies have a large tolerance to monatomic surface steps on the Ag(110) surface. The observed behaviour is explained in terms of strong intermolecular hydrogen bonding and a strong surface-mediated directionality, assisted by a sufficient degree of molecular backbone flexibility. In contrast, the same kind of step-edge crossing is not observed when the molecules are adsorbed on the isotropic Ag(111) or more reactive Cu(110) surfaces. On Ag(111), similar 1-D assemblies are formed to those on Ag(110), but they are oriented along the step edges. On Cu(110), the carboxylic groups of NDCA are deprotonated and form covalent bonds to the surface, a situation which is also achieved on Ag(110) by annealing to 200 ℃. These results show that the formation of particular self-assembled molecular nanostructures depends significantly on a subtle balance between the adsorbate-adsorbate and adsorbate-substrate interactions and that kinetic factors play an important role.

Keywords: hydrogen bonding, X-ray photoelectron spectroscopy, scanning tunnelling microscopy, Molecular self-assembly

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Publication history
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Publication history

Received: 08 February 2010
Revised: 29 April 2010
Accepted: 29 April 2010
Published: 01 June 2010
Issue date: July 2010

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© The Author(s) 2010

Acknowledgements

Acknowledgements

Eva Rauls is acknowledged for discussions and for providing the drawings of the NDCA molecules in Figs. 1 and 2. J. S. acknowledges funding from the European Commission through a Marie Curie Intra-European Fellowship. Funding from the Swedish Research Council (VR) is gratefully acknowledged.

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