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   Controlling crystallization kinetics is key to overcome the temperature–time dilemma in phase change materials employed for data storage. While the amorphous phase must be preserved for more than 10 years at slightly above room temperature to ensure data integrity, it has to crystallize on a timescale of several nanoseconds following a moderate temperature increase to near 2/3T_mto compete with other memory devices such as dynamic random access memory (DRAM). Here, a calorimetric demonstration that this striking variation in kinetics involves crystallization occurring either from the glassy or from the undercooled liquid state is provided. Measurements of crystallization kinetics of Ge₂Sb₂Te₅with heating rates spanning over six orders of magnitude reveal a fourfold decrease in Kissinger activation energy for crystallization upon the glass transition. This enables rapid crystallization above the glass transition temperatureT_g. Moreover, highly unusual for glass‐forming systems, crystallization at conventional heating rates is observed more than 50 °C belowT_g, where the atomic mobility should be vanishingly small.

    

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