熵调控GeTe菱方相—立方相转变及热电性能

Entropy regulation of rhombohedral-cubic phase transition and thermoelectric properties in GeTe

  • 摘要: GeTe作为典型的中温区热电材料,因其优异的热电性能而备受关注。然而,GeTe在室温下呈低对称性的菱方相,升温后转变为立方相。当相变温度处于器件服役温区时,两相间的热膨胀失配易引发热应力,从而降低器件的服役稳定性。此外,高对称性的立方相有利于提高能带简并度并促进价带汇聚,进而改善电子输运性能。因此,如何在室温下稳定GeTe立方相,已成为GeTe基热电材料结构设计与性能优化的关键问题。近年来,随着中高熵材料设计理念的发展,熵工程逐渐成为调控GeTe相结构的重要策略。引入多元组分所增加的构型熵、增强的局域无序以及改变的自由能竞争关系,能够抑制低温菱方畸变,促进高对称立方相在室温下的形成。实现室温立方相不仅有助于缓解相变诱发的热应力,还能通过提高晶体对称性、促进价带汇聚和增强声子散射,实现结构稳定性与热电性能的协同优化。本文综述熵驱动GeTe室温立方相的实现及其性能调控,系统总结GeTe的晶体结构特征及菱方相—立方相转变机制,探讨熵调控实现室温立方相的热力学基础及其对自由能竞争的影响,分析室温立方相对电子和热输运性能的作用,并归纳GeTe基材料中利用熵及高熵体系实现室温立方相的典型研究进展,最后对当前熵调控研究中的关键问题及未来发展方向进行展望。

     

    Abstract: GeTe, a typical mid-temperature thermoelectric material, has attracted extensive attention owing to its excellent thermoelectric performance. However, GeTe exists as a low-symmetry rhombohedral phase at room temperature and transforms into a cubic phase upon heating. When the phase-transition temperature falls within the operating range of thermoelectric devices, the mismatch in thermal expansion between the two phases can induce thermal stress, thereby compromising device stability. In addition, the cubic phase possesses higher crystal symmetry, which is beneficial for increasing band degeneracy and promoting valence-band convergence, thus improving electronic transport properties. Therefore, stabilizing the cubic phase of GeTe at room temperature has become a critical issue in the structural design and performance optimization of GeTe-based thermoelectric materials. In recent years, with the development of high-entropy material design concepts, entropy engineering has emerged as an effective strategy for regulating the phase structure of GeTe. The introduction of multiple elements increases configurational entropy, enhances local disorder, and alters relative Gibbs free energies, thereby weakening low-temperature rhombohedral distortion and promoting the formation of the high-symmetry cubic phase at room temperature. Realizing the cubic phase is expected to alleviate thermally induced stress associated with phase transitions. Furthermore, through enhanced crystal symmetry, valence-band convergence, and intensified phonon scattering, it enables the synergistic optimization of structural stability and thermoelectric performance. This review focuses on the entropy-driven stabilization of the cubic phase in GeTe and its effect on thermoelectric performance regulation. The crystal structure characteristics of GeTe and the mechanism of the rhombohedral-to-cubic phase transition are systematically summarized. The thermodynamic basis for entropy-regulated cubic phase stabilization and its influence on the competition of Gibbs free energies are then discussed. Furthermore, the effects of the cubic phase on electronic and thermal transport properties are analyzed, and recent representative advances in high-entropy-regulated GeTe-based materials are reviewed. Finally, key challenges and future directions for entropy-regulated GeTe-based thermoelectric materials are outlined.

     

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