The crystallization of amorphous Ge x Te 1-x (x= 0.36, 0.51, 0.63) films (50 nm) has been investigated by time resolved reflectivity, transmission electron microscopy, Raman spectroscopy and X-ray diffraction. The Ge-rich film has the highest crystallization temperature (354 C) with respect to both GeTe (180 C) and Te-rich samples (244 C). In non-stoichiometric films, the precipitation of the excess atomic species is the first step during the crystallization process: amorphous Ge and crystalline Te precipitates were detected in Ge and Te rich alloys, respectively. The atomic interdiffusivity was estimated to be~ 5× 10− 15 cm 2/s at 220 C in the Te-rich alloy and~ 4× 10− 14 cm 2/s in the Ge-rich film at 330 C. In both cases Tellurium is likely to be the diffusing species. This description accounts for the presence of amorphous Ge precipitates at the initial stage of the crystallization of the Ge rich alloy. The GeTe crystalline …