Role of Intrinsic Defects in Enhancing the Photoabsorption Capability of CuZn(2)AlSe(4)

[Image: see text] As a promising candidate for low-cost and eco-friendly thin-film photovoltaics, the emerging quaternary chalcogenide based solar cells have experienced rapid advances over the past decade. Here, we propose quaternary semiconducting chalcogenides CuZn(2)AlSe(4) (CZASe) through cross-substitutions (cation mutations). The nonexistence of imaginary modes in the entire Brillouin zone of CZASe represents the inherent dynamic stability of the system. The electronic, optical, and defect properties of stannite CZASe quaternary semiconducting material was systematically investigated using density functional theory calculations. We have found that the chemical-potential control is very important for growing good-quality crystals and also to avoid secondary-phase formations such as ZnSe, Al(2)ZnSe(4), and Cu(3)Se(2). The observed p-type conductivity is mainly due to antisite defect Cu(Zn), which has the lowest formation energy with a relatively deeper acceptor level than that of the Cu vacant site (V(Cu)). The electronic band structures of vacancies and antisite defects by means of hybrid functional calculations show energy band shifting and energy band narrowing or broadening, which eventually tunes the optical band gap and improves the solar energy-conversion performance of semiconducting CZASe. Our results suggest that the stannite CZASe quaternary chalcogenides could be promising candidates for the efficient earth-abundant thin-film solar cells.