Polymorphic phase transitions are common in crystalline solids. Recent studies suggest that phase transitions may also exist between two liquid forms with different entropy and structure. Such a liquid-liquid transition has been investigated in various substances including water, Al 2 O 3 -Y 2 O 3 and network glass formers. However, the nature of liquid-liquid transition is debated due to experimental difficulties in avoiding crystallization and/or measuring at high temperatures/pressures. Here we report the thermodynamic and structural evidence of a temperature-induced weak first-order liquid-liquid transition in a bulk metallic glassforming system Zr 41.2 Ti 13.8 Cu 12.5 Ni 10 Be 22.5 characterized by non-(or weak) directional bonds. Our experimental results suggest that the local structural changes during the transition induce the drastic viscosity changes without a detectable density anomaly. These changes are correlated with a heat capacity maximum in the liquid. Our findings support the hypothesis that the 'strong' kinetics (low fragility) of a liquid may arise from an underlying lambda transition above its glass transition.

In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid–liquid phase transition in the phase-change materials Ag4In3Sb67Te26 and Ge15Sb85 at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics.

A method to enhance the data transfer rate of eutectic Sb-Te phase-change recording media A striking anomaly in the viscosity of Te 85 Ge 15 alloys noted by Greer and coworkers from the work of Neumann et al. is reminiscent of the equally striking comparison of liquid tellurium and water anomalies documented long ago by Kanno et al. In view of the power laws that are used to fit the data on water, we analyze the data on Te 85 Ge 15 using the Speedy-Angell power-law form, and find a good account with a singularity T s only 25 K below the eutectic temperature. However, the heat capacity data in this case are not diverging, but instead exhibit a sharp maximum like that observed in fast cooling in the Molinero-Moore model of water. Applying the Adam-Gibbs viscosity equation to these calorimetric data, we find that there must be a fragile-to-strong liquid transition at the heat capacity peak temperature, and then predict the "strong" liquid course of the viscosity down to T g at 406 K (403.6 K at 20 K min À1 in this study). Since crystallization can be avoided by moderately fast cooling in this case, we can check the validity of the extrapolation by making a direct measurement of fragility at T g , using differential scanning calorimetric techniques, and then comparing with the value from the extrapolated viscosity at T g . The agreement is encouraging, and prompts discussion of relations between water and phase change alloy anomalies. V C 2015 AIP Publishing LLC. [http://dx.

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 2/3 Tm to 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 Ge2Sb2Te5 with 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 temperature Tg. Moreover, highly unusual for glass‐forming systems, crystallization at conventional heating rates is observed more than 50 °C below Tg, where the atomic mobility should be vanishingly small.

Abstract

The slow β relaxation is understood to be a universal feature of glassy dynamics. Its presence in bulk metallic glasses (BMGs) is evidence of a broad relaxation time spectrum that extends to deep within the glassy state. Despite the breadth of research devoted to this phenomenon, its microscopic origin is still not fully understood. The low-temperature aging behavior and atomic structural rearrangements of a Au 49 Cu 26.9 Si 16.3 Ag 5.5 Pd 2.3 BMG are investigated in the regime of the slow β relaxation by employing an ensemble of experimental techniques such as high-intensity synchrotron x-ray scattering, modulated differential scanning calorimetry (MDSC), dynamic mechanical analysis (DMA), impulse excitation, and dilatometry. Evidence of a distinct slow β-relaxation regime is seen in the form of (1) an excess wing of the DMA loss modulus beginning at ∼50• C, (2) a crossover effect of elastic modulus with isothermal aging at 50• C, and (3) a broad, nonreversing and largely irreversible sub-T g endotherm in the MDSC results. Atomic rearrangements occurring at the onset of the measured slow β-relaxation temperature regime were found to be confined mainly to the short-range order length scale while no significant atomic rearrangements occur on the length scale of the medium-range order. Furthermore, evidence is presented that suggests the crossover effect in Young's modulus is due to the evolution of chemical short-range order. These results support the emergent picture of a dynamically heterogeneous glassy structure, in which low-temperature relaxation occurs through atomic rearrangements confined mostly to the short-range order length scale.

Controlling a state of material between its crystalline and glassy phase has fostered many real-world applications. Nevertheless, design rules for crystallization and vitrification kinetics still lack predictive power. Here, we identify stoichiometry trends for these processes in phase change materials, i.e. along the GeTe-GeSe, GeTe-SnTe, and GeTe-Sb2Te3 pseudo-binary lines employing a pump-probe laser setup and calorimetry. We discover a clear stoichiometry dependence of crystallization speed along a line connecting regions characterized by two fundamental bonding types, metallic and covalent bonding. Increasing covalency slows down crystallization by six orders of magnitude and promotes vitrification. The stoichiometry dependence is correlated with material properties, such as the optical properties of the crystalline phase and a bond indicator, the number of electrons shared between adjacent atoms. A quantum-chemical map explains these trends and provides a blueprint to design crystallization kinetics.

Failure of classic equation linking diffusion and viscosity points to new thinking on switch kinetics of phase-change materials.