First-principles calculations reveal the n-type doping difficulties of group IIIA elements in zinc blende ZnS

At present, the n-type doping behavior of ZnS is still under debate. Some groups have reported that it is difficult to obtain low-resistivity n-type ZnS, while others think it is easy. Our first-principles calculations on the n-type doping of group IIIA elements strongly support the former viewpoint. We find that, although AlS−i, GaS−i, and InS−i are shallow donors, their formation energy is very high at the conduction band minimum (CBM). Thus they can not contribute to the n-type conductivity. Other impurities are all deep donors with high formation energy at the CBM, thus having no contributions either. We believe that our results can provide an understanding of the difficulties of n-type doping of ZnS.

► The LDA+U scheme is used to correct the band gap error. ► The formation energy and transition levels are calculated and discussed. ► Neutral and charged impurities in substitutional sites and interstitial sites are considered. ► Our results are in agreement with some experimental reports, and can provide an understanding of n-type doping difficulties of ZnS.