Defect energy levels and persistent luminescence in Cu-doped ZnS

[Display omitted] [Display omitted] Zinc sulfide (ZnS) based materials are widely used in many applications. Yet, due to a lack of detailed knowledge of defect energy levels, the electrical properties and luminescence mechanisms in the materials still give rise to debate. Here, we report a first-principles study of native point defects and impurities in zincblende ZnS using hybrid density-functional calculations. We find that cation and anion vacancies and antisite defects introduce deep defect levels in the band gap and can act as donors or acceptors depending on the position of the Fermi level. The substitutional impurity CuZn acts as a deep acceptor and thus does not contribute to p-type conductivity. Substitutional impurities AlZn and ClS, on the other hand, are shallow donors. More importantly, we identify the isolated (i.e., unassociated) CuZn as a source of the green luminescence observed in ZnS-based phosphors and CuZn–AlZn and CuZn–ClS defect complexes as sources of blue luminescence. The materials may have both green and blue emissions with the relative intensity dependent on the ratio between the unassociated defect and defect complex concentrations, which is also consistent with experimental observations.