Origin of the Disparity Between the Stability of Transmutated Mixcation and Mix-anion Compounds

Abstract

Abstract Transmutation is an efficient approach for material design. For example, ternary compound CuGaSe2 in chalcopyrite structure is a promising material for novel optoelectronic and thermoelectric device applications. It can be considered as formed from the binary host compound ZnSe in zinc-blende structure by cation transmutation (i.e., replacing two Zn by one Cu and one Ga). While cation-transmutated materials are common, anion-transmutated ternary materials are rare, for example, Zn2AsBr (i.e., replacing two Se by one As and one Br) is not reported. The physical origin for this puzzling disparity is unclear. In this work, we employ first-principles calculations to address this issue, and find that the distinct differences in stability between cation-transmutated (mix-cation) and anion-transmutated (mix-anion) compounds originate from their different trend of ionic radii as function of their ionic state, i.e., for cations, the radius decreases with the increasing ionic state, whereas for anions, the radius increase with the increasing absolute ionic state. Therefore, for mix-cation compounds, the strain energy and Coulomb energy can be simultaneously optimized to make these materials stable. In contrast, for mix-anion systems, minimization of Coulomb energy will increase the strain energy, thus the system becomes unstable or less stable. Thus, the trend of decreasing strain energy and Coulomb energy is consistent in mix-cation compounds, while it is opposite in mix-anion compounds. Furthermore, the study suggests that the stability strategy for mixanion compounds can be controlled by the ratio of ionic radii r 3/r 1, with a smaller ratio indicating greater stability. Our work, thus, elucidates the intrinsic stability trend of transmutated materials and provides guidelines for the design of novel ternary materials for various device applications.