Abstract 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 2/3Tmto 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 temperatureTg. Moreover, highly unusual for glass‐forming systems, crystallization at conventional heating rates is observed more than 50 °C belowTg, where the atomic mobility should be vanishingly small. 
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                    This content will become publicly available on March 20, 2026
                            
                            Controlling the Crystallization Kinetics of Low Loss Phase Change Material Sb 2 S 3
                        
                    
    
            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. 
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                            - Award ID(s):
- 2242925
- PAR ID:
- 10624063
- Publisher / Repository:
- Wiley-VCH GmbH
- Date Published:
- Journal Name:
- Advanced Physics Research
- ISSN:
- 2751-1200
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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