Thin film technology has reached a maturity to achieve conversion efficiencies of the order of 22%. Among thin films, CdTe-based photovoltaic modules represent 80% of the total production. Nonetheless, some issues concerning back-contact are still open. In industrial process a chemical etching is required in order to make the CdTe film surface rich in Te. The Te-excess is fundamental in order to form a stable telluride compound with copper and to obtain an ohmic, low-resistance back-contact. Moreover, the Te-excess hinders the fast diffusion of copper in CdTe and its achievement of the junction region, preventing the destruction of the device. In this paper we study a ZnTe:Cu buffer layer deposited onto a CdTe film, characterized by a naturally Te-rich surface obtained with a particular chlorine heat treatment without any chemical etching. Copper diffusion and the CdTe/ZnTe:Cu interface were studied by x-ray photoemission spectroscopy (SIPS) and time-of-flight secondary ion mass spectrometry (ToF- SIMS) to deeply analyze the intermixing phenomena and copper behavior inside polycrystalline CdTe film.