Composition Dependence of the Band Gap and Doping in Cu2O-Based Alloys as Predicted by an Extension of the Dilute-Defect Model

Tuning the optoelectronic properties through alloying is essential for semiconductor technology. Currently, mostly isovalent and isostructural alloys are used (e. g., groups IV and III-V), but a vast and unexplored space of novel functional materials is conceivable when considering more complex alloys by mixing aliovalent and heterostructural constituents. The real challenge lies in the quantitative property prediction for such complex alloys to guide their experimental exploration. We develop an approach to predict compositional dependence of both band-structure and electrical properties from ab initio calculations by extending the conventional dilute-defect model to higher (alloy) concentrations. Considering alloying of aliovalent (Mg, Zn, Cd) cations and isovalent anions (S, Se) into Cu2O, we predict tunability of band-gap energies and doping levels over a wide range, including the type conversion from p to n type. Initial synthesis and characterization of Zn- and Se-substituted Cu2O support the defect model, suggesting these alloys as promising novel oxide-semiconductor materials.