Surface-Induced Optimal Packing of Two-Dimensional Molecular Networks

Guillaume Copie, Fabrizio Cleri, Younes Makoudi, Christophe Krzeminski, Maxime Berthe, Frédéric Cherioux, Frank Palmino, and Bruno Grandidier
Phys. Rev. Lett. 114, 066101 – Published 13 February 2015
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Abstract

High-density packing in organic crystals is usually associated with an increase of the coordination between molecules. Such a concept is not necessarily extended to two-dimensional molecular networks self-assembled on a solid surface, for which we demonstrate the key role of the surface in inducing the optimal packing. By a combination of scanning tunneling microscopy experiments and multiscale computer simulations, we study the phase transition between two polymorphs. We find that, contrary to intuition, the structure with the lowest packing fraction corresponds to the highest molecular coordination number, due to the competition between surface and intermolecular forces. Having the lowest free energy, this structure spreads out as the most stable polymorph over a wide range of molecular concentrations.

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  • Received 4 June 2014

DOI:https://doi.org/10.1103/PhysRevLett.114.066101

© 2015 American Physical Society

Authors & Affiliations

Guillaume Copie1, Fabrizio Cleri1,*, Younes Makoudi2, Christophe Krzeminski3, Maxime Berthe3, Frédéric Cherioux2, Frank Palmino2, and Bruno Grandidier3

  • 1Institut d’Electronique Microélectronique et Nanotechnologie (IEMN), Université de Lille I, CNRS, UMR 8520, Avenue Poincaré BP60069, 59652 Villeneuve d’Ascq, France
  • 2Institut FEMTO-ST, Université de Franche-Comté, CNRS, ENSMM, 15B Avenue des Montboucons, F-25030 Besançon cedex, France
  • 3Département ISEN, Institut d’Electronique Microélectronique et Nanotechnologie (IEMN), CNRS, UMR 8520, 41 boulevard Vauban, 59046 Lille, France

  • *fabrizio.cleri@univ-lille1.fr

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Issue

Vol. 114, Iss. 6 — 13 February 2015

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