The interest in understanding and controlling the properties of two-dimensional materials (2DMs) has fostered in the last years a significant and multidisciplinary research effort involving condensed matter physics and materials science. Although 2DMs have been investigated with a wide set of different experimental and theoretical methodologies, experiments carried out with surface-science based techniques were essential to elucidate many aspects of the properties of this family of materials. In particular, synchrotron-based X-ray photoelectron spectroscopy (XPS) has been playing a central role in casting light on the properties of 2DMs, providing an in-depth and precise characterization of these materials and helping to elucidate many elusive and intricate aspects related to them. XPS was crucial, for example, in understanding the mechanism of growth of several 2DMs at surfaces and in identifying the parameters governing it. Moreover, the chemical sensitivity of this technique is crucial in obtaining knowledge about functionalized 2DMs and in testing their behavior in several model chemical reactions. The achievements accomplished so far in this field have reached a maturity point for which a recap of the milestones is desirable. In this review, we will showcase relevant examples of studies on 2DMs for which synchrotron-based XPS, in combination with other techniques and state-of-the-art theoretical modeling of the electronic structure and of the growth mechanisms, was essential to unravel many aspects connected to the synthesis and properties of 2DMs at surfaces. The results highlighted herein and the methodologies followed to achieve them will serve as a guidance to researchers in testing and comparing their research outcomes and in stimulating further investigations to expand the knowledge of the broad and versatile 2DMs family.

在过去几年中，对理解和控制二维材料 (2DM) 特性的兴趣促进了涉及凝聚态物理和材料科学的重要的多学科研究工作。尽管已经使用各种不同的实验和理论方法对 2DM 进行了研究，但使用基于表面科学的技术进行的实验对于阐明此类材料的许多特性至关重要。特别是，基于同步加速器的 X 射线光电子能谱 (XPS) 在阐明 2DM 的特性方面一直发挥着核心作用，提供了对这些材料的深入和精确的表征，并有助于阐明许多难以捉摸和复杂的相关方面给他们。XPS 至关重要，例如，了解表面上几种 2DM 的生长机制并确定控制它的参数。此外，该技术的化学敏感性对于获取有关功能化 2DM 的知识以及测试它们在多种模型化学反应中的行为至关重要。迄今为止在该领域取得的成就已达到成熟点，因此需要对里程碑进行回顾。在这篇综述中，我们将展示 2DM 研究的相关示例，其中基于同步加速器的 XPS 结合其他技术以及电子结构和生长机制的最先进理论模型，对于解开许多问题至关重要与表面 2DM 的合成和特性相关的方面。