Ohmic contacts to thin-film CdS/CdTe photovoltaic devices have been formed using a two-layer contact interface of undoped ZnTe (ZnTe) and Cu-doped ZnTe (ZnTe:Cu), followed by Ni or Ti as an outer metallization. Secondary ion mass spectroscopy (SIMS) is used to study Cu diffusion within this back-contact structure, and also, to monitor Cu diffusion from the contact into the CdTe. When Ni metallization is used, the ZnTe:Cu layer becomes increasingly depleted of Cu, and Ni diffusion into the ZnTe:Cu increases as the contact deposition temperature increases from 100&hthinsp;°C to 300&hthinsp;°C. Cu depletion is not observed when Ni is replaced with Ti. Diffusion of Cu from the ZnTe:Cu layer into the ZnTe layer also increases with contact deposition temperature, and produces a buildup of Cu at the ZnTe/CdTe interface. High-mass resolution SIMS indicates that, although Cu levels in the CdTe remain low, Cu diffusion from the contact proceeds into the CdTe layer and toward the CdTe/CdS junction region. ©1999 American Institute of Physics.