Influence of Vacancy Defects on the Interfacial Structural and Optoelectronic Properties of ZnO/ZnS Heterostructures for Photocatalysis

Hybrid density functional theory has been employed to study the influence of interfacial oxygen (O), sulfur (S) and zinc (Zn) vacancies on the optoelectronic properties of ZnO/ZnS heterostructure. The results show that the O, S, and Zn vacancies can decrease cell volume of the ZnO/ZnS heterostructure, leading to slight deformation from the perfect heterostructure. The quasi-band gap of ZnO/ZnS heterostructure is remarkably reduced compared to the ZnO surface. Hence, the visible light response is enhanced in ZnO/ZnS heterostructure, which can be further improved by creating an interfacial S or O vacancy. Moreover, the removal of S or O atoms can generate lone electrons in the system, which can enhance n-type conductivity of the heterostructure. The O and S vacancies improve the contribution of the atomic orbitals of Zn_ZnO (Zn atom in ZnO), Zn_ZnS (Zn atom in ZnS), S and O to the valence band maximum (VB) of the heterostructure; while the Zn-vacancy remarkably improves the contribution of S states to the conduction band minimum (CB). The resultant type-II band alignment and large difference between the migration speed of electrons and holes can efficiently separate the photogenerated electron-hole pairs. The CB edge positions are more negative than the redox potentials of CO₂/CO and H₂O/H₂, and the VB edge positions are more positive than the redox potential of O₂/H₂O. Hence, all the systems under investigation can be potentially used as efficient photocatalysts for various applications like CO₂ reduction and water splitting.