Yb,Sb共掺杂GeTe的制备及其增强的热电性能

doi:10.15541/jim20260108

摘要/Abstract

摘要： GeTe基热电材料存在电、热输运参数难以协同优化的瓶颈,严重限制其热电性能与实际应用。因此,本文在前期Yb掺杂实现能带收敛的基础上,进一步引入Sb掺杂以提升其热电性能。采用高能球磨结合热压烧结工艺,制备出系列Ge_0.98-_xSb_xYb_0.02Te(x=0~0.06)合金。Sb掺杂可有效降低材料的载流子迁移率与电子热导率,同时诱发微米级富Yb第二相析出。该富Yb第二相与Sb掺杂引入的点缺陷和晶格畸变协同作用,构建了高效的多尺度声子散射网络,显著抑制晶格热传导,使材料总热导率从2.13 W·m^-1·K^-1降至1.55 W·m^-1·K^-1。此外,Sb掺杂提升了载流子有效质量,保障功率因子维持在较高水平,其中Ge_0.93Sb_0.05Yb_0.02Te在800 K时达到2.19的峰值热电优值(ZT)。本研究通过Sb掺杂实现了载流子迁移率与声子散射的协同优化,提升了GeTe基热电材料性能,为该类材料的实际应用提供了理论与实验支撑。

关键词: GeTe, 热电材料, Sb掺杂, 晶格热导率, 载流子迁移率, 声子散射, 优值ZT

Abstract: The bottleneck of GeTe-based thermoelectric materials lies in the difficulty in synergistically optimizing electrical and thermal transport parameters, which severely limits their thermoelectric performance and practical applications. Therefore, this study introduces Sb doping to enhance their thermoelectric performance, building upon the previous achievement of band convergence through Yb doping. A series of Ge_0.98-_xSb_xYb_0.02Te (x=0-0.06) alloys were prepared via high-energy ball milling and hot-press sintering. It is found that Sb doping not only reduces carrier mobility and electronic thermal conductivity but also triggers the precipitation of Yb-rich micron-scale secondary phases which establish a multiscale phonon-scattering network along with the point defects and lattice distortion induced by Sb. Consequently, a significant suppression of lattice thermal conductivity is achieved, leading to a reduction in total thermal conductivity from 2.13 to 1.55 W·m^-1·K^-1. Combined with an increased effective mass that maintains a high power factor, Ge_0.93Sb_0.05Yb_0.02Te attains a peak ZT value of 2.19 at 800 K. This study achieved a synergistic effect to enhance both carrier mobility and phonon scattering through Sb doping, optimizing the performance of GeTe-based thermoelectric materials and providing theoretical and experimental support for the practical application of such materials.

Key words: GeTe, thermoelectric material, Sb doping, lattice thermal conductivity, carrier mobility, phonon scattering, figure of merit ZT value.

中图分类号:

TB34

杜豪睿, 长俊刚, 蔡芳共, 随友朋, 袁永林, 唐瑗, 高培, 雷晓波, 匡泉, 张勤勇. Yb,Sb共掺杂GeTe的制备及其增强的热电性能[J]. 无机材料学报, DOI: 10.15541/jim20260108.

DU Haorui, CHANG Jungang, CAI Fanggong, SUI Youpeng, YUAN Yonglin, TANG Yuan, GAO Pei, LEI Xiaobo, KUANG Quan, ZHANG Qinyong. Yb, Sb Co-doped GeTe: Preparation and Enhanced Thermoelectric Performance[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260108.

参考文献

[1] BELL L E.Cooling, heating, generating power, and recovering waste heat with thermoelectric systems.Science, 2008, 321(5895): 1457.
[2] ZHANG Q, WANG H, LIU W,et al. Enhancement of thermoelectric figure-of-merit by resonant states of aluminium doping in lead selenide. Energy & Environmental Science, 2012, 5(1): 5246.
[3] ZHANG Q, YANG S, ZHANG Q,et al. Effect of aluminum on the thermoelectric properties of nanostructured PbTe. Nanotechnology, 2013, 24(34): 345705.
[4] SMORODIN B L, VELARDE M G.Convective instability of an Ohmic liquid layer in an unsteady thermal field.Physics of Fluids, 2008, 20(4): 044101.
[5] CAI F, CHEN X, YUAN G,et al. Sulfur simultaneously acts as pore-forming agent and doping agent to improve the thermoelectric properties of Bi₂Te_2.7Se_0.3. Journal of Alloys and Compounds, 2020, 819: 153384.
[6] FALEEV S V, LEONARD F.Theory of enhancement of thermoelectric properties of materials with nanoinclusions.Physical Review B—Condensed Matter and Materials Physics, 2008, 77(21): 214304.
[7] HE W, WANG D, WU H,et al. High thermoelectric performance in low-cost SnS_0.91Se_0.09 crystals. Science, 2019, 365(6460): 1418.
[8] LIU W D, WANG D Z, LIU Q,et al. High performance GeTe based thermoelectrics: from materials to devices. Advanced Energy Materials, 2020, 10(19): 2000367.
[9] CAO T, SHI X L, ZOU J,et al. Advances in conducting polymer-based thermoelectric materials and devices. Microstructures, 2021, 1: 2021007.
[10] YUE L, FANG T, ZHENG S,et al. Cu/Sb codoping for tuning carrier concentration and thermoelectric performance of GeTe-based alloys with ultralow lattice thermal conductivity. ACS Applied Energy Materials, 2019, 2(4): 2596.
[11] TAN M, LIU W D, SHI X L,et al. Anisotropy control-induced unique anisotropic thermoelectric performance in the n-type Bi₂Te_2.7Se_0.3 thin films. Small Methods, 2019, 3(11): 1900582.
[12] WANG L, FANG S, LI J,et al. Anomalous enhancement of thermoelectric performance in GeTe with specific interaxial angle and atomic displacement synergy. Cell Reports Physical Science, 2022, 3(9): 101009.
[13] JIANG B, WANG W, LIU S,et al. High figure-of-merit and power generation in high-entropy GeTe based thermoelectrics. Science, 2022, 377(6602): 208.
[14] TSAI Y, WEI P, CHANG L,et al. Compositional fluctuations locked by athermal transformation yielding high thermoelectric performance in GeTe. Advanced Materials, 2021, 33(1): 2005612.
[15] CHRISTAKUDI T A, PLACHKOVA S K, CHRISTAKUDIS G C.Thermoelectric power of (GeTe)_1-_x(Bi₂Te₃)_x solid solutions. Physica Status Solidi (a), 1995, 147(1): 211.
[16] LEWIS J E.The defect structure of non-stoichiometric germanium telluride from magnetic susceptibility measurements.Physica Status Solidi (b), 1970, 38(1): 131.
[17] DAMON D H, LUBELL M S, MAZELSKY R.Nature of the defects in germanium telluride.Journal of Physics and Chemistry of Solids, 1967, 28(3): 520.
[18] ZHANG Q, SONG Q, WANG X,et al. Deep defect level engineering: a strategy of optimizing the carrier concentration for high thermoelectric performance. Energy & Environmental Science, 2018, 11(4): 933.
[19] ZHAO Y, DYCK J S, HERNANDEZ B M,et al. Enhancing thermoelectric performance of ternary nanocrystals through adjusting carrier concentration. Journal of the American Chemical Society, 2010, 132(14): 4982.
[20] PEI Y, LALONDE A D, HEINZ N A,et al. Stabilizing the optimal carrier concentration for high thermoelectric efficiency. Advanced Materials, 2011, 23(47): 5674.
[21] BHANDARI C M, ROWE D M.Optimization of carrier concentration//ROWE D M, ed. CRC Handbook of Thermoelectrics. Boca Raton: CRC Press, 1995: 43-54.
[22] WAN C, WANG Y, WANG N,et al. Development of novel thermoelectric materials by reduction of lattice thermal conductivity. Science and Technology of Advanced Materials, 2010, 11(4): 044306.
[23] HANUS R, AGNE M T, RETTIE A J E,et al. Lattice softening significantly reduces thermal conductivity and leads to high thermoelectric efficiency. Advanced Materials, 2019, 31(21): 1900108.
[24] CAYLOR J C, COONLEY K, STUART J,et al. Enhanced thermoelectric performance in PbTe based superlattice structures. Applied Physics Letters, 2005, 87(2): 023105.
[25] FAN Z, WANG H, WU Y,et al. Thermoelectric high entropy alloys with low lattice thermal conductivity. RSC Advances, 2016, 6(57): 52164.
[26] PERUMAL S, ROYCHOWDHURY S, NEGI D S,et al. High thermoelectric performance of p-type Ge_1-_xSb_xTe. Chemistry of Materials, 2015, 27(20): 7171.
[27] LI J, ZHANG X, LIN S,et al. Realizing high thermoelectric performance of GeTe by Sb doping and Se alloying. Chemistry of Materials, 2017, 29(2): 605.
[28] KHAN A U, ORABI R A R A, PAKDEL A,et al. Sb doping of metallic CuCr₂S₄ toward improved thermoelectric properties. Chemistry of Materials, 2017, 29(7): 2988.
[29] BHATTACHARYA S, POPE A L, LITTLETON R T,et al. Effect of Sb doping on thermoelectric properties of TiNiSn_1-_xSb_x. Applied Physics Letters, 2000, 77(16): 2476.
[30] YANG Y, PRADEL K C, JING Q,et al. Thermoelectric nanogenerators based on Sb doped ZnO nanobelts. ACS Nano, 2012, 6(8): 6984.
[31] ZHOU Z, YANG J, JIANG Q,et al. Multiple effects of Bi doping in SnTe thermoelectrics. Journal of Materials Chemistry A, 2016, 4(34): 13171.
[32] YANG L, CHEN Z G, HONG M,et al. n-type Bi doped PbTe nanocubes with enhanced thermoelectric performance. Nano Energy, 2017, 31: 105.
[33] TANI J, KIDO H.Thermoelectric properties of Bi doped Mg₂Si semiconductors.Physica B: Condensed Matter, 2005, 364(1-4): 218.
[34] NSHIMYIMANA E, SU X, XIE H,et al. Non equilibrium process for high thermoelectric performance Sb doped GeTe. Science Bulletin, 2018, 63(11): 717.
[35] LOU A, LIU Q B, FU H H.Lone pair electrons and bond anharmonicity in Ge₂Y₂ thermoelectrics.Physical Review B, 2022, 105(7): 075431.
[36] DU B, ZHANG R, CHEN K,et al. Impact of lone pair electrons on lattice thermal conductivity of CuSbS₂. Journal of Materials Chemistry A, 2017, 5(7): 3249.
[37] LI C, SONG H, DAI Z,et al. High thermoelectric performance in Sb doped GeTe via carrier concentration manipulation. Materials, 2022, 15(2): 406.
[38] QI X, YU Y, XU X,et al. Enhanced thermoelectric performance in GeTe-Sb₂Te₃ pseudo binary. Materials Today Physics, 2021, 21: 100507.
[39] ZHANG F, HE S, LI R,et al. Vacancy engineering and band manipulation in Sb doped SnTe alloys. Applied Physics Letters, 2021, 119(17): 173903.
[40] TAN G, STOUMPOS C C, WANG S,et al. Roles of Sb and S in regulating thermoelectric properties of PbTe. Advanced Energy Materials, 2017, 7(18): 1700099.
[41] DOW H S, OH M W, KIM B S,et al. Effect of Ag or Sb addition on thermoelectric properties of PbTe. Journal of Applied Physics, 2010, 108(11): 113703.
[42] HORAK J, CERMAK K, KOUDELKA L.Antisite defects in doped Sb₂Te₃ and Bi₂Te₃.Journal of Physics and Chemistry of Solids, 1986, 47(8): 805.
[43] SNYDER G J, SNYDER A H, WOOD M,et al. Weighted mobility. Advanced Materials, 2020, 32(25): 2001537.
[44] QIN B, HE W, ZHAO L D.Estimation of thermoelectric performancevia weighted mobility. Journal of Materiomics, 2020, 6(4): 671.
[45] LI M, SUN Q, XU S D,et al. Optimizing electronic quality factor toward high‐performance Ge_1-_x-_yTa_xSb_yTe thermoelectrics: the role of transition metal doping. Advanced Materials, 2021, 33(40): 2102575.
[46] GUO Z, ZHANG Q, WANG H,et al. Bi--Zn codoping in GeTe synergistically enhances band convergence and phonon scattering for high thermoelectric performance. Journal of Materials Chemistry A, 2020, 8(41): 21642.
[47] ZHENG Z, SU X, DENG R,et al. 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, 2018, 140(7): 2673.
[48] GAO W, LIU Z, ZHANG W,et al. Improved thermoelectric performance of GeTe via efficient yttrium doping. Applied Physics Letters, 2021, 118(3): 033902.
[49] SHUAI J, SUN Y, TAN X,et al. Manipulating the Ge vacancies and Ge precipitates through Cr doping for realizing the high‐performance GeTe thermoelectric material. Small, 2020, 16(13): 1906921.
[50] ZHANG C, YAN G, WANG Y,et al. Grain boundary complexions enable a simultaneous optimization of electron and phonon transport leading to high‐performance GeTe thermoelectric devices. Advanced Energy Materials, 2023, 13(3): 2203361