The phase transition temperature and crystallization kinetics of phase-change materials (PCMs) are crucial characteristics for their performance, data retention, and reliability in memory devices. Herein, the crystallization behavior and kinetics of a compositionally optimized, N-doped Ge-rich Ge–Sb–Te alloy (GGST) in the slow crystallization regime are systematically investigated using synchrotron x-ray diffraction (XRD) in situ during heat treatment. Uniform thin films (50, 25, 10, and 5 nm) of initially amorphous N-doped GGST are investigated. The specimens were heated up to 450 °C at a rate of 2 °C/min to estimate crystallization onsets by quantifiying the crystallized quantity during material transformation from the XRD patterns. Subsequent isothermal anneals have been performed to assess crystallization behavior and activation energies. Nucleation-controlled crystallization that progresses in two steps is observed, together with the emergence of Ge preceding cubic Ge2Sb2Te5, with a mild dependence of crystallization temperature on film thickness that is inverse to what has been observed in other systems. Ge and GST crystallization may be described occurring in three-time stages: (i) an incubation period; (ii) a fast growth period; and (iii) a very slow-growth period. Very high activation energies (between 3.5 and 4.3 eV) for each phase are found for the incubation time t0. The activation energy for Ge in the fast growth regime is close to the one reported for the crystallization of pure Ge films. In the case of Ge, the incubation time is strongly thickness-dependent, which may have important consequences for the scaling of memories fabricated with this class of materials.

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