We examine the effects of several intrinsic defects on the magnetic behavior of ZnS nanostructures using hybrid density functional theory to gain insights into d0 ferromagnetism. Previous studies have predicted that the magnetism is due to a coupling between partially filled defect states. By taking into account the electronic correlations, we find an additional splitting of the defect states in Zn vacancies and thus the possibility of gaining energy by preferential filling of hole states, establishing ferromagnetism between spin polarized S 3p holes. We demonstrate a crucial role of neutral S vacancies in promoting ferromagnetism between positively charged S vacancies. S dangling bonds on the nanoparticle surface also induce ferromagnetism.

DOI: 10.1039/c4ra06237j.