Luminescence of undoped commercial ZnS crystals: A critical review and new evidence on the role of impurities using photoluminescence and electrical transient spectroscopy

Bulk undoped ZnS materials exhibit relatively bright yet diverse luminescence behavior, which has, in recent years, been attributed to intrinsic defects. However, the luminescence also resembles that of doped materials, implying a role of impurities. Luminescence features have also been attributed to oxygen impurities causing defect clusters or energy band anti-crossing. Thus, this study couples optical and electrical techniques, such as band edge transmission, photoluminescence (PL), PL excitation, radioluminescence, thermoluminescence, optical deep level transient spectroscopy, and photoinduced current transient spectroscopy, to explore the identity of defect levels. ZnS materials studied are commercial single crystals made by physical vapor transport, high-pressure Bridgman, and powder processing. These undoped bulk ZnS exhibit luminescence behavior similar to that of reported doped ZnS powders (10−4 to 10−2 mol. % doping for luminescent materials). Dopants (such as Al, Cl, Cu, and Ag) are also commonly found impurities in ZnS; hence, it is reasonable to believe they have a role in the luminescence of nominally undoped ZnS. By comparing the variation in optical and electrical properties between samples to the processing method and the rich literature on intentionally doped ZnS, this study shows a possible dominant contribution of impurities and impurity-containing defects on the luminescence of bulk “undoped” ZnS. Hence, there is no need to resort to complex mechanisms to explain the luminescence, but rather the metal and halide impurities and their defect complexes determine the main characteristics of luminescence in this wide-bandgap semiconductor.