Understanding the physical and chemical processes in which local interactions lead to ordered structures is of particular relevance to the realization of supramolecular architectures on surfaces. While spectacular patterns have been demonstrated on metal surfaces, there have been fewer studies of the spontaneous organization of supramolecular networks on semiconductor surfaces, where the formation of covalent bonds between organics and adatoms usually hamper the diffusion of molecules and their subsequent interactions with each other. However, the saturation of the dangling bonds at a semiconductor surface is known to make them inert and offers a unique way for the engineering of molecular patterns on these surfaces. This review describes the physicochemical properties of the passivated B-Si(111)-(√3x√3) R30° surface, that enable the self-assembly of molecules into a rich variety of extended and regular structures on silicon. Particular attention is given to computational methods based on multi-scale simulations that allow to rationalize the relative contribution of the dispersion forces involved in the self-assembled networks observed with scanning tunneling microscopy. A summary of state of the art studies, where a fine tuning of the molecular network topology has been achieved, sheds light on new frontiers for exploiting the construction of supramolecular structures on semiconductor surfaces.

了解局部相互作用导致有序结构的物理和化学过程与表面上超分子体系结构的实现特别相关。尽管已经在金属表面上证明了惊人的图案，但是对半导体表面上超分子网络的自发组织的研究却很少，在有机表面上，有机物和原子之间的共价键形成通常会阻碍分子的扩散以及它们之间的后续相互作用。然而，已知悬空键在半导体表面处的饱和会使它们呈惰性，并为工程化这些表面上的分子图案提供了独特的方法。这篇评论描述了钝化的B-Si（111）-（√3x√3）R30°表面的理化性质，使分子能够自组装成硅上的各种扩展和规则结构。应特别注意基于多尺度模拟的计算方法，该方法可以合理化用扫描隧道显微镜观察到的自组装网络中所涉及的色散力的相对贡献。在对分子网络拓扑结构进行微调的最新技术研究的总结中，揭示了利用半导体表面上超分子结构的构建的新领域。应特别注意基于多尺度模拟的计算方法，该方法可以合理化用扫描隧道显微镜观察到的自组装网络中所涉及的色散力的相对贡献。在对分子网络拓扑结构进行微调的最新技术研究的总结中，揭示了利用半导体表面上超分子结构的构建的新领域。应特别注意基于多尺度模拟的计算方法，该方法可以合理化用扫描隧道显微镜观察的自组装网络中所涉及的色散力的相对贡献。在对分子网络拓扑结构进行微调的最新技术研究的总结中，揭示了利用半导体表面上超分子结构的构建的新领域。