Direct evidence for abrupt postcrystallization germanium precipitation in thin phase-change films of Sb–15at.% Ge

We present evidence for the instability in the crystalline (metallic) state of binary Te-free phase-change Ge–Sb thin films considered for integration into nonvolatile nanosized memory cells. We find that while the amorphous (semiconducting) phase of eutectic Sb–15at.% Ge is very robust until Sb crystallization at 240°C, at about 350°C, germanium rapidly precipitates out. Ge precipitation, visualized directly with transmission electron microscopy, is exothermic and is found to affect the films’ reflectivity, resistance, and stress. It converts melting into a two-step process, which may seriously impact the switching reliability of a device.