We report a detailed study of molecular beam epitaxial growth of ZnS films on bare and arsenic-passivated vicinal Si(100) surfaces. This study elucidates the initiation of microtwinning and stacking-fault defects on double-stepped substrate surfaces. The study also sheds light on the function of arsenic passivation in reducing crystal defects in ZnS epitaxial layers. Three substrate surfaces, Si(100) 2×1, Si(100):As 2×1, and Si(100):As 1×2, were used for the ZnS epitaxial growth studies. Adsorption experiments were performed to demonstrate the chemical passivation effect of an arsenic overlayer. Reflection high-energy electron diffraction was used to study growth modes and the epitaxial relationship of the ZnS layers to the substrates. Transmission electron microscopy was used to study the crystal-defect structures. Secondary ion mass spectroscopy was used to determine the chemical profiles of the heteroepitaxial interfaces of ZnS layers grown on arsenic-passivated surfaces. One of the main results demonstrated by this work is that thin ZnS films can be grown epitaxially with much better crystal quality on As-passivated Si surfaces than on bare Si surfaces. © 1997 American Institute of Physics.