Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
Centre for Advanced 2D Materials and Graphene Research Centre, National University of Singapore, 6 Science Drive 2, 117546 Singapore, Singapore.
Phys Rev Lett. 2015 Jan 30;114(4):046801. doi: 10.1103/PhysRevLett.114.046801. Epub 2015 Jan 28.
Surface reactions with oxygen are a fundamental cause of the degradation of phosphorene. Using first-principles calculations, we show that for each oxygen atom adsorbed onto phosphorene there is an energy release of about 2 eV. Although the most stable oxygen adsorbed forms are electrically inactive and lead only to minor distortions of the lattice, there are low energy metastable forms which introduce deep donor and/or acceptor levels in the gap. We also propose a mechanism for phosphorene oxidation involving reactive dangling oxygen atoms and we suggest that dangling oxygen atoms increase the hydrophilicity of phosphorene.
表面与氧气的反应是导致黑磷降解的一个基本原因。通过第一性原理计算，我们表明，对于吸附在黑磷上的每个氧原子，大约有 2eV 的能量释放。尽管最稳定的吸附氧形式是电惰性的，只导致晶格的微小变形，但也存在低能量的亚稳形式，它们在能带隙中引入深施主和/或受主能级。我们还提出了一个涉及反应性悬空氧原子的黑磷氧化机制，并表明悬空氧原子增加了黑磷的亲水性。
