Special methods were developed to grow Si/ZnS/Si heterostructures for the purpose of developing silicon-based quantum devices. An arsenic passivation technique was used on silicon surfaces for the growth of ZnS. The effectiveness of this surface passivation was demonstrated by the improved crystal quality and decreased heterostructural interface-state density. A two-step growth method was developed for the epitaxial growth of silicon on ZnS surfaces. In this method the normal silicon epitaxial growth was preceded by a solid phase epitaxy process. Single crystal films of silicon were successfully grown on ZnS surfaces. Our discussion addresses two key issues: crystal defects and the density of interface states. The results of RHEED (reflection high energy electron diffraction), C-V (capacitance voltage), and SIMS (secondary ion mass spectroscopy) measurements are presented.