First-Principles Study on the Role of Cu and Cl-Based Dopants in NiO

Utilization of wide band gap oxide-based materials in thin-film solar energy technologies has increased in recent years. Among the numerous candidate oxide materials, NiO has shown many desirable optoelectronic properties that are applicable to thin-film PV technologies such as cadmium telluride PV. However, one critical factor requiring further investigation is the p-type doping behavior of NiO, specifically when the cadmium telluride solar cell undergoes conventional processes such as copper doping and chlorine-based activation treatment. The previous literature has shown a large degree of variability in hole concentrations in NiO when copper is used as the primary dopant. This study uses first-principles computational modeling based on density functional theory coupled with defect equilibria calculations to quantitatively explore the role of copper and chlorine-based extrinsic dopants in the p-type doping activity of NiO. The study reveals the importance of extrinsic dopants and their binding interactions with nickel vacancies to effectively p-dope NiO. It is suggested that both the formation of VNi + CuNi and VNi + ClO defect pairs under a supersaturated state of NiO are potential mechanisms for increasing hole densities. On the other hand, the production of 2CuNi severely limits the effectiveness of p-doping in NiO, even in the presence of the aforementioned defect pairs. The study provides a guideline for experimentalists interested in using copper or chlorine species to understand how to controllably p-dope NiO during thin-film synthesis.