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Abstract Optoelectronics are crucial for developing energy‐efficient chip technology, with phase‐change materials (PCMs) emerging as promising candidates for reconfigurable components in photonic integrated circuits, such as nonvolatile phase shifters. Antimony sulfide (Sb₂S₃) stands out due to its low optical loss and considerable phase‐shifting properties, along with the non‐volatility of both phases. This study demonstrates that the crystallization kinetics of Sb₂S₃can be switched from growth‐driven to nucleation‐driven by altering the sample dimension from bulk to film. This tuning of the crystallization process is critical for optical switching applications requiring control over partial crystallization. Calorimetric measurements with heating rates spanning over six orders of magnitude, reveal that, unlike conventional PCMs that crystallize below the glass transition, Sb₂S₃exhibits a measurable glass transition prior to crystallization from the undercooled liquid (UCL) phase. The investigation of isothermal crystallization kinetics provides insights into nucleation rates and crystal growth velocities while confirming the shift to nucleation‐driven behavior at reduced film thicknesses—an essential aspect for effective device engineering. A fundamental difference in chemical bonding mechanisms was identified between Sb₂S₃, which exhibits covalent bonding in both material phases, and other PCMs, such as GeTe and Ge₂Sb₂Te₅, which demonstrate pronounced bonding alterations upon crystallization. 

Dynamic heterogeneity is a fundamental characteristic of glasses and undercooled liquids. The heterogeneous nature causes some of the key features of systems’ dynamics such as the temperature dependence of nonexponentiality and spatial enthalpy fluctuations. Commonly used phenomenological models such as Tool–Narayanaswamy–Moynihan (TNM) and Kovacs–Aklonis–Hutchinson–Ramos fail to fully capture this phenomenon. Here we propose a model that can predict the temperature-dependent nonexponential behavior observed in glass-forming liquids and glasses by fitting standard differential scanning calorimetry curves. This model extends the TNM framework of structural relaxation by introducing a distribution of equilibrium fictive temperature (Tfe) that accounts for heterogeneity in the undercooled liquid. This distribution is then frozen at the glass transition to account for the heterogeneous nature of the glass dynamics. The nonexponentiality parameter βKWW is obtained as a function of temperature by fitting the Kohlrauch-Williams-Watts (KWW) equation to the calculated relaxation function for various organic and inorganic undercooled liquids and glasses. The calculated temperature dependent βKWW shows good agreement with the experimental ones. We successfully model the relaxation dynamics far from equilibrium for two silicate systems that the TNM model fails to describe, confirming that temperature dependent nonexponentiality is necessary to fully describe these dynamics. The model also simulates the fluctuation of fictive temperature δTf during isothermal annealing with good qualitative agreement with the evolution of enthalpy fluctuation reported in the literature. We find that the evolution of enthalpy fluctuation during isothermal annealing heavily depends on the cooling rate, a dependence that was not previously emphasized. 

Owing to their ability for fast switching and the large property contrast between the crystalline and amorphous states that permits multi-level data storage, in-memory computing and neuromorphic computing, the investigation of phase change materials (PCMs) remains a highly active field of research. Yet, the continuous increase in electrical resistance (called drift) observed in the amorphous phase has so far hindered the commercial implementation of multi-level data storage. It was recently shown that the resistance drift is caused by aging-induced structural relaxation of the glassy phase, which is accompanied by a simultaneous decrease in enthalpy and fictive temperature. This implies that resistance is related to enthalpy relaxation. While the resistance is known to drift even at room temperature and below, evidence for enthalpy relaxation at room temperature in amorphous PCMs is still missing. Here, we monitor changes in enthalpy induced by long-term room-temperature aging in a series of PCMs. Our results demonstrate the simultaneity of resistance drift and enthalpy relaxation at room temperature, and thus provide further insights into the mechanism of resistance drift and its possible remediation. 

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). 

Pyramidal antireflective structures were produced by hot embossing single- and double-sides of an amorphous GeSe₄optical element. The optical performances were measured across the wavelength range from 2 µm to 15 µm. The transmittance at normal incident angle was increased up to 75.6% and 79.8% for single and double-side embossing respectively. The experimental results were in close agreement with simulation performed using the rigorous coupled-wave analysis (RCWA). Theoretical models also predicted well the transmittance changes as a function of incident angle from 0 ° to 50 ° at a fixed laser wavelength of 5.1 µm. A Fabry-Perot interferometer consisting of two single surface embossed samples is proposed.