Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers

Amandine Bellec, Claire Arrigoni, Guillaume Schull, Ludovic Douillard, Cöline Fiorini-Debuisschert, Fabrice Mathevet, David Kreher, Andrö Jean Attias, Fabrice Charra

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Abstract

The temperature and concentration dependences of the self-assembly onto graphite from solution of a series of molecular building blocks able to form nanoporous structures are analyzed experimentally by in situ scanning tunneling microscopy. It is shown that the commonly observed coexistence of dense and nanoporous domains results from kinetic blockades rather than a thermodynamic equilibrium. The ripening can be favored by high densities of domain boundaries, which can be obtained by cooling the substrate before the nucleation and growth. Then ripening at higher-temperature yields large defect-free domains of a single structure. This thermodynamically stable structure can be either the dense or the nanoporous one, depending on the tecton concentration in the supernatant solution. A sharp phase transition from dense to honeycomb structures is observed at a critical concentration. This collective phenomenon is explained by introducing interactions between adsorbed molecules in the thermodynamic description of the whole system.

Original languageEnglish
Article number124702
JournalJournal of Chemical Physics
Volume134
Issue number12
DOIs
Publication statusPublished - Mar 28 2011

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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    Bellec, A., Arrigoni, C., Schull, G., Douillard, L., Fiorini-Debuisschert, C., Mathevet, F., Kreher, D., Attias, A. J., & Charra, F. (2011). Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers. Journal of Chemical Physics, 134(12), [124702]. https://doi.org/10.1063/1.3569132