Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers.
Solution-growth kinetics and thermodynamics of nanoporous self-assembled molecular monolayers.
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DOI：
10.1063/1.3569132
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发表时间：
2011-03
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通讯作者：
A. Bellec;Claire Arrigoni;G. Schull;L. Douillard;C. Fiorini-Debuisschert;F. Mathevet;D. Kreher;A. Attias;F. Charra
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作者：
A. Bellec;Claire Arrigoni;G. Schull;L. Douillard;C. Fiorini-Debuisschert;F. Mathevet;D. Kreher;A. Attias;F. Charra
通过原位扫描隧道显微镜实验分析了一系列能够形成纳米多孔结构的分子构建块的溶液在石墨上的自组装的温度和浓度依赖性。结果表明，通常观察到的共存的致密和纳米多孔域的结果从动力学封锁，而不是一个热力学平衡。成熟可以通过高密度的畴界来促进，畴界可以通过在成核和生长之前冷却衬底来获得。然后在更高的温度下熟化产生单一结构的大的无缺陷域。这种结晶稳定的结构可以是致密的或纳米多孔的，这取决于上层溶液中的tecton浓度。在临界浓度下观察到从致密到蜂窝结构的急剧相变。通过在整个系统的热力学描述中引入吸附分子之间的相互作用来解释这种集体现象。
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.