First-Principles Cluster Expansion Study Of Functionalization Of Black Phosphorene Via Fluorination And Oxidation

Predicting the ground states for surface adsorption is a challenging problem because the number of degrees of freedom involved in the process is very high. Most of the studies deal with some specific arrangements of adsorbates on a given surface, but very few of them actually attempt to find the ground states for different adatom coverage. In this work, we show the effectiveness of the cluster expansion method to predict the "ground states" resulting from chemisorption of oxygen and fluorine atom on the surface of monolayer black phosphorus or phosphorene. For device applications, we find that in addition to band-gap tuning, controlled chemisorption can change the unique anisotropic carrier effective mass for both the electrons and holes and even rotate them by 90 degrees, which can be useful for exploring unusual quantum Hall effect and electronic devices based on phosphorene.