Shriber Pola, Samanta Atanu, Nessim Gilbert Daniel, Grinberg Ilya
Department of Chemistry , Bar-Ilan University , Ramat Gan , Israel 52900.
J Phys Chem Lett. 2018 Apr 5;9(7):1759-1764. doi: 10.1021/acs.jpclett.8b00055. Epub 2018 Mar 23.
Black phosphorus (BP) is a layered semiconductor with outstanding properties, making it a promising candidate for optoelectronic and other applications. BP synthesis is an intriguing task largely due to the insufficient understanding of the synthesis mechanism. In this work, we use density functional theory calculations to examine BP and its precursor red phosphorus as they are formed from P building blocks. Our results suggest that, without external effects such as pressure or addition of a catalyst, the precursor is energetically favored in the initial steps of the synthesis, even though BP is the more stable allotrope. The higher energy of BP is dictated by its 2D geometry that gives rise to the higher number of high-energy strained bonds at the edge compared to the 1D geometry of red phosphorus. The elucidated BP formation pathway provides a natural explanation for the effectiveness of the recently discovered Sn/I catalyst used in BP synthesis.
黑磷（BP）是一种具有出色性能的层状半导体，这使其成为光电子及其他应用领域颇具潜力的候选材料。BP的合成是一项引人关注的任务，很大程度上是因为对合成机理的理解不足。在这项工作中，我们使用密度泛函理论计算来研究BP及其前驱体红磷，它们由磷构建单元形成。我们的结果表明，在没有压力或添加催化剂等外部作用的情况下，尽管BP是更稳定的同素异形体，但前驱体在合成的初始步骤中在能量上更具优势。BP较高的能量是由其二维几何结构决定的，与红磷的一维几何结构相比，这种结构在边缘处产生了更多高能应变键。所阐明的BP形成途径为最近发现的用于BP合成的Sn/I催化剂的有效性提供了一个自然的解释。
