With the rapid development of scanning probe microscopy, it has become possible to study polymerization processes on suitable surfaces at the atomic level and in real space. In the two-dimensional confinement of a surface, polymerization reactions can give rise to the formation of unprecedented polymers with unique structures and properties, not accessible in solution. After a little over one decade since the discovery of covalent on-surface polymerization, we give an overview of the field, analyse the crucial aspects and critically reflect on the status quo. Specifically, we provide some general considerations about fundamental mechanisms as well as kinetics and thermodynamics of on-surface polymerization processes. The important role of the surface is detailed in view of its ability to control polymer formation with regard to structure, dimensionality and composition. Furthermore, examples that allow for locally induced polymerization are highlighted. Finally, we provide an analysis of scientific challenges in the field and outline future prospects.

中文翻译：

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共价表面聚合。

随着扫描探针显微镜的快速发展，在原子水平和真实空间中研究合适表面上的聚合过程成为可能。在表面的二维约束中，聚合反应会导致形成前所未有的具有独特结构和特性的聚合物，而这种独特的结构和特性是无法在溶液中获得的。自发现共价表面聚合反应以来的十多年，我们对这一领域进行了概述，分析了关键方面并批判性地反映了现状。具体来说，我们提供了一些有关表面聚合过程的基本机理以及动力学和热力学的一般考虑。考虑到表面在结构方面控制聚合物形成的能力，表面的重要作用得到了详细说明，尺寸和组成。此外，突出了允许局部引发聚合的例子。最后，我们提供了对该领域科学挑战的分析，并概述了未来的前景。