Bi-Mg-W共掺杂实现GeTe基热电材料超低晶格热导率
Bi-Mg-W Co-Doping Enables Ultralow Lattice Thermal Conductivity in GeTe-Based Thermoelectric Materials
DOI: 10.12677/ms.2026.164072, PDF,   
作者: 南嘉俊, 李 松, 彭菩保, 张玉晶, 唐国栋*：南京理工大学材料科学与工程学院，江苏 南京；詹敏言：三峡大学湖北科创学院(三峡)，湖北 宜昌
关键词: 热电材料；碲化锗；晶格热导率；功率因子；热电优值；Thermoelectric Materials； GeTe； Lattice Thermal Conductivity； Power Factor； Figure of Merit
摘要: GeTe因其顶尖的热电性能、环境友好特性而备受广泛关注。本研究证实，通过在GeTe样品中共掺杂Bi、Mg、W，可以显著提升热电性能。Bi、W元素作为电子供体，可以大大优化过量的载流子浓度，将载流子浓度调整至最佳范围。同时，Bi、Mg元素可以引起能带收敛从而优化GeTe电子能带结构，使得塞贝克系数显著提升。Bi、Mg、W与Ge的大小差异较大，引发了强烈的应变涨落，以及掺杂引入的大量点缺陷增强了声子散射，最终最优样品Ge0.937Bi0.04Mg0.02W0.003Te在673 K实现了0.356 W·m−1·K−1的超低晶格热导率。通过电声性能的协同调控，Ge0.937Bi0.04Mg0.02W0.003Te在823 K获得了高达2.11的峰值ZT，400~823 K的平均ZT达到1.5。
Abstract: GeTe has garnered extensive attention owing to its state-of-the-art thermoelectric performance, and environmental benignity. In this study, it is demonstrated that the thermoelectric properties of GeTe can be significantly enhanced through the co-doping of Bi, Mg, and W elements. As electron donors, Bi and W elements can effectively optimize the excessive carrier concentration, adjusting it to the optimal range. Meanwhile, Bi and Mg elements are capable of inducing band convergence to refine the electronic band structure of GeTe, resulting in a remarkable improvement in the Seebeck coefficient. The substantial differences in atomic sizes between Bi/Mg/W and Ge give rise to intense strain fluctuations, and the numerous point defects introduced by doping further strengthen phonon scattering. Ultimately, the optimal sample Ge0.937Bi0.04Mg0.02W0.003Te achieves an ultralow lattice thermal conductivity of 0.356 W·m−1·K−1 at 673 K. Through the synergistic regulation of electronic and phonon transport properties, Ge0.937Bi0.04Mg0.02W0.003Te attains a peak thermoelectric figure of merit (ZT) of up to 2.11 at 823 K, with an average ZT of 1.5 in the temperature range of 400~823 K.
文章引用：南嘉俊, 李松, 彭菩保, 詹敏言, 张玉晶, 唐国栋. Bi-Mg-W共掺杂实现GeTe基热电材料超低晶格热导率[J]. 材料科学, 2026, 16(4): 50-61. https://doi.org/10.12677/ms.2026.164072

参考文献

[1] Gelbstein, Y., Davidow, J., Girard, S.N., Chung, D.Y. and Kanatzidis, M. (2013) Controlling Metallurgical Phase Separation Reactions of the Ge0.87Pb0.13Te Alloy for High Thermoelectric Performance. Advanced Energy Materials, 3, 815-820. [Google Scholar] [CrossRef] 
[2] Back, S.Y., Yun, J.H., Cho, H., et al. (2021) High Thermoelectric Performance by Chemical Potential Tuning and Lattice Anharmonicity in GeTe1−xIx Compounds. Inorganic Chemistry Frontiers, 8, 1205-1214. [Google Scholar] [CrossRef] 
[3] Liu, Z., Gao, W., Zhang, W., et al. (2020) High Power Factor and Enhanced Thermoelectric Performance in Sc and Bi Co-Doped GeTe: Insights into the Hidden Role of Rhombohedral Distortion Degree. Advanced Energy Materials, 10, Article 2002588. [Google Scholar] [CrossRef] 
[4] Xing, T., Zhu, C., Song, Q., et al. (2021) Ultralow Lattice Thermal Conductivity and Superhigh Thermoelectric Figure‐of‐Merit in (Mg, Bi) Co‐Doped GeTe. Advanced Materials, 33, Article 2008773. [Google Scholar] [CrossRef] [PubMed]
[5] Li, M., Xu, S.D., Lyu, W.Y., et al. (2023) Unravelling Effective-Medium Transport and Interfacial Resistance in (CaTe)x(GeTe)100-x Thermoelectrics. Chemical Engineering Journal, 452, Article 139269. [Google Scholar] [CrossRef] 
[6] Zheng, Z., Su, X., Deng, R., Stoumpos, C., Xie, H., Liu, W., et al. (2018) Rhombohedral to Cubic Conversion of GeTe via MnTe Alloying Leads to Ultralow Thermal Conductivity, Electronic Band Convergence, and High Thermoelectric Performance. Journal of the American Chemical Society, 140, 2673-2686. [Google Scholar] [CrossRef] [PubMed]
[7] Dou, Y., Li, J., Xie, Y., Wu, X., Hu, L., Liu, F., et al. (2021) Lone-Pair Engineering: Achieving Ultralow Lattice Thermal Conductivity and Enhanced Thermoelectric Performance in Al-Doped GeTe-Based Alloys. Materials Today Physics, 20, Article 100497. [Google Scholar] [CrossRef] 
[8] Zhang, Q., Ying, P., Farrukh, A., Gong, Y., Liu, J., Huang, X., et al. (2024) High Wide-Temperature-Range Thermoelectric Performance in GeTe through Hetero-Nanostructuring. Acta Materialia, 276, Article 120132. [Google Scholar] [CrossRef] 
[9] Hong, M., Wang, Y., Liu, W., Matsumura, S., Wang, H., Zou, J., et al. (2018) Arrays of Planar Vacancies in Superior Thermoelectric Ge1−x−yCdxBiyTe with Band Convergence. Advanced Energy Materials, 8, Article 1801837. [Google Scholar] [CrossRef] 
[10]  Liu, C., Zhang, Z., Peng, Y., Li, F., Miao, L., Nishibori, E., et al. (2023) Charge Transfer Engineering to Achieve Extraordinary Power Generation in GeTe-Based Thermoelectric Materials. Science Advances, 9, eadh0713. [Google Scholar] [CrossRef] [PubMed]
[11] Samanta, M., Ghosh, T., Arora, R., Waghmare, U.V. and Biswas, K. (2019) Realization of Both n-and p-Type GeTe Thermoelectrics: Electronic Structure Modulation by AgBiSe2 Alloying. Journal of the American Chemical Society, 141, 19505-19512. [Google Scholar] [CrossRef] [PubMed]
[12] Zhang, Q., Ti, Z., Zhang, Y., Nan, P., Li, S., Li, D., et al. (2023) Ultralow Lattice Thermal Conductivity and High Thermoelectric Performance in Ge1-x-yBixCayTe with Ultrafine Ferroelectric Domain Structure. ACS Applied Materials & Interfaces, 15, 21187-21197. [Google Scholar] [CrossRef] [PubMed]
[13] Wang, J.S. (2020) First Principles Investigation on Anomalous Lattice Shrinkage of W Alloyed Rock Salt Gete. Journal of Physics and Chemistry of Solids, 137, Article 109220. [Google Scholar] [CrossRef] 
[14] Wu, D., Xie, L., Xu, X. and He, J. (2019) High Thermoelectric Performance Achieved in GeTe-Bi2Te3 Pseudo-Binary via Van Der Waals Gap-Induced Hierarchical Ferroelectric Domain Structure. Advanced Functional Materials, 29, Article 1806613. [Google Scholar] [CrossRef] 
[15] Dong, J., Sun, F., Tang, H., Pei, J., Zhuang, H., Hu, H., et al. (2019) Medium-Temperature Thermoelectric Gete: Vacancy Suppression and Band Structure Engineering Leading to High Performance. Energy & Environmental Science, 12, 1396-1403. [Google Scholar] [CrossRef] 
[16] Xing, T., Song, Q., Qiu, P., Zhang, Q., Xia, X., Liao, J., et al. (2019) Superior Performance and High Service Stability for GeTe-Based Thermoelectric Compounds. National Science Review, 6, 944-954. [Google Scholar] [CrossRef] [PubMed]
[17] Zhang, Q., Ti, Z., Zhu, Y., Zhang, Y., Cao, Y., Li, S., et al. (2021) Achieving Ultralow Lattice Thermal Conductivity and High Thermoelectric Performance in Gete Alloys via Introducing Cu2Te Nanocrystals and Resonant Level Doping. ACS Nano, 15, 19345-19356. [Google Scholar] [CrossRef] [PubMed]
[18] Jin, Y., Xiao, Y., Wang, D., Huang, Z., Qiu, Y. and Zhao, L. (2019) Realizing High Thermoelectric Performance in Gete through Optimizing Ge Vacancies and Manipulating Ge Precipitates. ACS Applied Energy Materials, 2, 7594-7601. [Google Scholar] [CrossRef] 
[19] Shuai, J., Sun, Y., Tan, X. and Mori, T. (2020) Manipulating the Ge Vacancies and Ge Precipitates through Cr Doping for Realizing the High-Performance Gete Thermoelectric Material. Small, 16, Article 1906921. [Google Scholar] [CrossRef] [PubMed]
[20] Tsai, Y.F., Ho, M.Y., Wei, P.C., et al. (2022) Hierarchical Twinning and Light Impurity Doping Enable High-Performance GeTe Thermoelectrics. Acta Materialia, 222, Article 117406. [Google Scholar] [CrossRef] 
[21] Tan, X., Zhang, F., Zhu, J., et al. (2023) High-Power Factor Enabled by Efficient Manipulation Interaxial Angle for Enhancing Thermoelectrics of GeTe-Cu2Te Alloys. ACS Applied Materials & Interfaces, 15, 9315-9323. [Google Scholar] [CrossRef] [PubMed]
[22] Rodenkirchen, C., Cagnoni, M., Jakobs, S., et al. (2020) Employing Interfaces with Metavalently Bonded Materials for Phonon Scattering and Control of the Thermal Conductivity in TAGS‐x Thermoelectric Materials. Advanced Functional Materials, 30, Article 1910039. [Google Scholar] [CrossRef] 
[23] Hong, M., Chen, Z., Yang, L., et al. (2018)Realizing zT of 2.3 in Ge1−x−ySbxInyTe via Reducing the Phase‐Transition Temperature and Introducing Resonant Energy Doping. Advanced Materials, 30, Article 1705942. [Google Scholar] [CrossRef] [PubMed]
[24] Lou, Q., Xu, X., Huang, Y., et al. (2020) Excellent Thermoelectric Performance Realized in p-Type Pseudolayered Sb2Te3 (GeTe)12 via Rhenium Doping. ACS Applied Energy Materials, 3, 2063-2069. [Google Scholar] [CrossRef] 
[25] Zhang, T., Deng, S., Zhao, X., Ruan, X., Qi, N., Chen, Z., et al. (2022) Regulation of Ge Vacancies through Sm Doping Resulting in Superior Thermoelectric Performance in GeTe. Journal of Materials Chemistry A, 10, 3698-3709. [Google Scholar] [CrossRef] 
[26] Zhang, X., Li, J., Wang, X., Chen, Z., Mao, J., Chen, Y., et al. (2018) Vacancy Manipulation for Thermoelectric Enhancements in GeTe Alloys. Journal of the American Chemical Society, 140, 15883-15888. [Google Scholar] [CrossRef] [PubMed]

为你推荐