The effect of electronic orbital interactions on p-type doping tendency in ZnO series: First-principles calculations

The electronic structures and optical properties of B3 ZnO series of Zn_4X_4-yM_y(X=O, S, Se or Te; M=N, Sb, Cl or I; y=0 or 1) are studied by first-principles calculations using a pseudopotential plane-wave method. The results show that Zn d-X p orbital interactions play an important role in the p-type doping tendency in zinc-based II-VI semiconductors. In ZnX, with increasing atomic number of X, Zn d-X p orbital interactions decrease and Zn s-X p orbital interactions increase. Additionally, substituting group-V elements for X will reduce the Zn d-X p orbital interactions while substituting group-VII elements for X will increase the Zn d-X p orbital interactions. The results also show that group-V-doped ZnX and group-VII-doped ZnX exhibit different optical behaviours due to their different orbital interaction effects.