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

Amandine Bellec 1 Claire Arrigoni 2 Guillaume Schull 3 Ludovic Douillard 2 Céline Fiorini-Debuisschert 2 Fabrice Mathevet 4 David Kreher 5 André-Jean Attias 5 Fabrice Charra 2 
2 LEPO - Laboratoire d'Electronique et nanoPhotonique Organique
SPEC - UMR3680 - Service de physique de l'état condensé, IRAMIS - Institut Rayonnement Matière de Saclay
4 LCP - Chimie des polymères
UPMC - Université Pierre et Marie Curie - Paris 6, IPCM - Institut Parisien de Chimie Moléculaire, CNRS - Centre National de la Recherche Scientifique : UMR7610
Abstract : The temperature and concentration dependences of the self-assembly onto graphite from solution of a series of molecular building blocks able to form nanoporousstructures are analyzed experimentally by in situscanning 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.
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Submitted on : Monday, December 5, 2016 - 4:50:04 PM
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Amandine Bellec, Claire Arrigoni, Guillaume Schull, Ludovic Douillard, Céline Fiorini-Debuisschert, et al.. Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers. Journal of Chemical Physics, American Institute of Physics, 2011, 134 (12), ⟨10.1063/1.3569132⟩. ⟨cea-01409138⟩



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