Modeling Off-Stoichiometry Materials with a High-Throughput Ab- Initio Approach

Predicting material properties of off-stoichiometry systems remains a long-standing and formidable challenge in rational materials design. A proper analysis of such systems by means of a supercell approach requires the exhaustive consideration of all possible superstructures, which can be a time-consuming process. On the contrary, the use of quasirandom approximants, although very computationally effective, implicitly bias the analysis toward disordered states with the lowest site correlations. Here, we propose a novel framework designed specifically to investigate stoichiometrically driven trends of disordered systems (i.e., having partial occupation and/or disorder in the atomic sites). At the heart of the approach is the identification and analysis of unique supercells of a virtually equivalent stoichiometry to the disordered material. We employ Boltzmann statistics to resolve system-wide properties at a high-throughput (HT) level. To maximize efficiency and accessibility, we integrated the method within the automatic HT computational framework AFLOW. As proof of concept, we apply our approach to three systems of interest, a zinc chalcogenide (ZnS1−xSex), a wide-gap oxide semiconductor (MgxZn1−xO), and an iron alloy (Fe1−xCux), at various stoichiometries. These systems exhibit properties that are highly tunable as a function of composition, characterized by optical bowing and linear ferromagnetic behavior. Not only are these qualities successfully predicted, but additional insight into underlying physical mechanisms is revealed.