Many phase change materials (PCMs) are found to crystallize without exhibiting a glass transition endotherm upon reheating. In this paper, we review experimental evidence revealing that these PCMs and likely other hyperquenched molecular and metallic systems can crystallize from the glassy state when reheated at a standard rate. Among these evidences, PCMs annealed below the glass transition temperature T g exhibit slower crystallization kinetics despite an increase in the number of sub-critical nuclei that should promote the crystallization speed. Flash calorimetry uncovers the glass transition endotherm hidden by crystallization and reveals a distinct change in kinetics when crystallization switches from the glassy to the supercooled liquid state. The resulting T g value also rationalizes the presence of the pre- T g relaxation exotherm ubiquitous of hyperquenched systems. Finally, the shift in crystallization temperature during annealing exhibits a non-exponential decay that is characteristic of structural relaxation in the glass. Modeling using a modified Turnbull equation for nucleation rate supports the existence of sub- T g fast crystallization and emphasizes the benefit of a fragile-to-strong transition for PCM applications due to a reduction in crystallization at low temperature (improved data retention) and increasing its speed at high temperature (faster computing).
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Exploring “No Man's Land”—Arrhenius Crystallization of Thin‐Film Phase Change Material at 1 000 000 K s −1 via Nanocalorimetry
Non‐volatile phase‐change memory (PCM) devices are based on phase‐change materials such as Ge2Sb2Te5 (GST). PCM requires critically high crystallization growth velocity (CGV) for nanosecond switching speeds, which makes its material‐level kinetics investigation inaccessible for most characterization methods and remains ambiguous. In this work, nanocalorimetry enters this “no‐man's land” with scanning rate up to 1 000 000 K s−1(fastest heating rate among all reported calorimetric studies on GST) and smaller sample‐size (10–40 nm thick) typical of PCM devices. Viscosity of supercooled liquid GST (inferred from the crystallization kinetic) exhibits Arrhenius behavior up to 290 °C, indicating its low fragility nature and thus a fragile‐to‐strong crossover at ≈410 °C. Thin‐film GST crystallization is found to be a single‐step Arrhenius process dominated by growth of interfacial nuclei with activation energy of 2.36 ± 0.14 eV. Calculated CGV is consistent with that of actual PCM cells. This addresses a 10‐year‐debate originated from the unexpected non‐Arrhenius kinetics measured by commercialized chip‐based calorimetry, which reports CGV 103−105higher than those measured using PCM cells. Negligible thermal lag (<1.5 K) and no delamination is observed in this work. Melting, solidification, and specific heat of GST are also measured and agree with conventional calorimetry of bulk samples.
more » « less- Award ID(s):
- 1809573
- NSF-PAR ID:
- 10369564
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Interfaces
- Volume:
- 9
- Issue:
- 23
- ISSN:
- 2196-7350
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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