(GeTe)nBi2Te3的结构与热电性能研究

doi:10.15541/jim20200252

摘要/Abstract

摘要：

在GeTe-Bi₂Te₃赝二元系统中, (GeTe)_n(Bi₂Te₃)_m化合物往往具有较低的晶格热导率, 但其中很多组分的热电性能尚未得到系统研究。本研究通过熔融、淬火、退火结合放电等离子烧结工艺制备了一系列(GeTe)_nBi₂Te₃(n=10, 11, 12, 13, 14)单相多晶样品, 并对其相组成和热电性能进行表征和研究。掺杂Bi₂Te₃可以显著增强点缺陷声子散射, 大幅度降低材料的晶格热导率, 在723 K时, (GeTe)₁₃Bi₂Te₃样品的总热导率低至1.63 W?m ^-1?K ^-1。此外, 掺杂Bi₂Te₃和调控GeTe的相对含量, 提高了材料的载流子有效质量, 即使在较高的载流子浓度下, 样品依然保持较高的塞贝克系数和功率因子, 在723 K, (GeTe)₁₃Bi₂Te₃样品获得最大的功率因子为2.88×10 ^-3 W?m ^-1?K ^-2, 最终(GeTe)₁₃Bi₂Te₃样品在723 K获得的最大ZT值达到1.27, 较未掺杂的GeTe样品提高了16%。

关键词: GeTe, Bi₂Te₃掺杂, 结构, 热电性能

Abstract:

In general, (GeTe)_n(Bi₂Te₃)_m compounds in GeTe-Bi₂Te₃ pseudo-binary system possess a relatively low thermal conductivity, however, the thermoelectric properties of these compounds have not been evaluated systematically. In this study, a series of single-phase (GeTe)_nBi₂Te₃ (n=10, 11, 12, 13, 14) compounds were prepared by a melting-quenching-annealing process combined with spark plasma sintering. The phase compositions and thermoelectrical properties of these samples were characterized. It is found that doping with Bi₂Te₃ intensifies the phonon scattering and significantly reduces the lattice thermal conductivities of these samples, producing a low total thermal conductivity of 1.63 W?m ^-1?K ^-1 at 723 K for (GeTe)₁₃Bi₂Te₃ compound. Moreover, the effective mass of these compounds is enhanced through adjustment of the relative amount of Bi₂Te₃ and GeTe. Therefore, the Seebeck coefficient and power factor of these samples remain superior even at high carrier concentration. At 723 K, the maximum power factor of (GeTe)₁₃Bi₂Te₃ compound is 2.88×10 ^-3 W?m ^-1?K ^-2 and the maximum ZT of (GeTe)₁₃Bi₂Te₃is 1.27, which is 16% higher than that of pristine GeTe.

Key words: GeTe, Bi₂Te₃doping, structure, thermoelectric property

中图分类号:

TB34/O482.6

杨枭, 苏贤礼, 鄢永高, 唐新峰. (GeTe)_nBi₂Te₃的结构与热电性能研究[J]. 无机材料学报, 2021, 36(1): 75-80.

YANG Xiao, SU Xianli, YAN Yonggao, TANG Xinfeng. Structures and Thermoelectric Properties of (GeTe)_nBi₂Te₃[J]. Journal of Inorganic Materials, 2021, 36(1): 75-80.

图/表 5

图1 (GeTe)nBi2Te3(n=10~14)化合物的粉末XRD图谱

Fig. 1 Powder XRD patterns of (GeTe)nBi2Te3(n=10~14) compounds

图2 (GeTe)nBi2Te3样品((a~d)n=10, (e~h)n=14)抛光面的(a, e)背散射电子图像和(b, f) Ge, (c, g) Te, (d, h) Bi元素面分布图

Fig. 2 (a, e) Back-scattering electron (BSE) images and (b, f)Ge, (c, g)Te and (d, h) Bi elemental distributions of the polished surfaces for (GeTe)nBi2Te3 samples ((a-d) n=10, (e-h) n=14)

图3 (GeTe)nBi2Te3的(a)电导率、(b)塞贝克系数随温度的变化曲线, (c)Pisarenko曲线, (d)迁移率与载流子浓度的关系

Fig. 3 Temperature dependence of (a) electrical conductivity, (b) Seebeck coefficient, (c) Pisarenko plots, (d) room temperature carrier mobility as a function of the carrier concentration for (GeTe)nBi2Te3

图4 (GeTe)nBi2Te3系列样品随温度变化的功率因子, 插图为723 K时系列样品的功率因子与载流子浓度的关系

Fig. 4 Temperature dependence of the power factor for (GeTe)nBi2Te3 compounds with inset showing the corresponding relationship between carrier concentration and power factor at 723 K

图5 (GeTe)nBi2Te3系列样品随温度变化的(a)总热导率和(b)晶格热导率, (c)样品的热电性能优值ZT随温度变化曲线

Fig. 5 Temperature dependence of (a) total thermal conductivity κ, (b) lattice thermal conductivity κL and (c) figure of merit ZT for (GeTe)nBi2Te3

参考文献 22

[1]	ROWE D M. CRC Handbook of thermoelectrics. New York: CRC Press, 1995: 7-17.
[2]	ROYCHOWDHURY S, SAMANTA M, PERUMAL S ,et al. Germanium chalcogenide thermoelectrics: electronic structure modulation and low lattice thermal conductivity. Chemistry of Materials, 2018,30(17):5799-5813.
[3]	HONG M, ZOU J, CHEN Z G . Thermoelectric GeTe with diverse degrees of freedom having secured superhigh performance. Advanced Materials, 2019,31(14):1-23.
[4]	PERUMAL S, ROYCHOWDHURY S, BISWAS K . High performance thermoelectric materials and devices based on GeTe. Journal of Materials Chemistry C, 2016,4(32):7520-7536.
[5]	OKAMOTO H. Ge-Te(Germanium-Tellurium). Journal of Phase Equilibria, 2000,21(5):496.
[6]	LEWIS J E . The defect structure of non-stoichiometric germanium telluride from magnetic susceptibility measurements. Physica Status Solidi (B), 1970,38(1):131-140.
[7]	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):2673-2686.
[8]	DONG J, SUN F H, TANG H ,et al. Medium-temperature thermoelectric GeTe: vacancy suppression and band structure engineering leading to high performance. Energy and Environmental Science, 2019,12(4):1396-1403.
[9]	PERUMAL S, ROYCHOWDHURY S, BISWAS K . Reduction of thermal conductivity through nanostructuring enhances the thermoelectric figure of merit in Ge₁-_xBi_xTe. Inorganic Chemistry Frontiers, 2016
	3(1):125-132.
[10]	PERUMAL S, BELLARE P, SHENOY U S ,et al. Low thermal conductivity and high thermoelectric performance in Sb and Bi codoped GeTe: complementary effect of band convergence and nanostructuring. Chemistry of Materials, 2017,29(24):10426-10435.
[11]	PERUMAL S, ROYCHOWDHURY S, NEGI D S ,et al. High thermoelectric performance and enhanced mechanical stability of P-type Ge₁. _xS. _xTe Chemistry of Materials, 2015,27(20):7171-7178.
[12]	WUTTIG M, YAMADA N . Phase-change materials for rewriteable data storage. Nature Materials, 2007,6(11):824-832.
[13]	ROSENTHAL T, SCHNEIDER M N, STIEWE C ,et al. Real structure and thermoelectric properties of GeTe-rich germanium antimony tellurides. Chemistry of Materials, 2011,23(19):4349-4356.
[14]	XU X, XIE L, LOU Q ,et al. Boosting the thermoelectric performance of pseudo-layered Sb₂Te₃( GeTe)_n via vacancy engineering. Advanced Science, 2018,5(12):1801514-1801520.
[15]	KOSUGA A, NAKAI K, MATSUZAWA M ,et al. Crystal structure, microstructure, and thermoelectric properties of GeSb₆Te₁₀ prepared by spark plasma sintering. Journal of Alloys and Compounds, 2015,618:463-468.
[16]	ROSENTHAL T, URBAN P, NIMMRICH K ,et al. Enhancing the thermoelectric properties of germanium antimony tellurides by substitution with selenium in compounds Ge_nSb₂(Te_1-_xSe_x)_n₊₃ (0≤ x≤0.5; n≥7). Chemistry of Materials, 2014,26(8):2567-2578.
[17]	SCHNEIDER M N, BIQUARD X, STIEWE C ,et al. From metastable to stable modifications - in situ laue diffraction investigation of diffusion processes during the phase transitions of (GeTe)_nSb₂Te₃(6<n<15) crystals. Chemical Communications, 2012,48(16):2192-2194.
[18]	SHELIMOVA L E, KONSTANTINOV P P, KARPINSKY O G ,et al. X-ray diffraction study and electrical and thermal transport properties of the nGeTe. mBi₂Te₃ homologous series compounds. Journal of Alloys and Compounds, 2001,329(1/2):50-62.
[19]	LI J, ZHANG C, FENG Y ,et al. Effects on phase transition and thermoelectric properties in the Pb-doped GeTe-Bi₂Te₃ alloys with thermal annealing. Journal of Alloys and Compounds, 2019,808:151747-151755.
[20]	WU D, ZHAO L D, HAO S ,et al. Origin of the high performance in GeTe-based thermoelectric materials upon Bi₂Te₃ doping. Journal of the American Chemical Society, 2014,136(32):11412-11419.
[21]	LI J, CHEN Z, ZHANG X , , et al. Electronic origin of the high thermoelectric performance of GeTe among the P-type group IV monotellurides. NPG Asia Materials, 2017, 9(3): e353-1-8.
[22]	HAZAN E, MADAR N, PARAG M ,et al. Effective electronic mechanisms for optimizing the thermoelectric properties of GeTe-rich alloys. Advanced Electronic Materials, 2015,1(11):1-7.

(GeTe)_nBi₂Te₃的结构与热电性能研究

Structures and Thermoelectric Properties of (GeTe)_nBi₂Te₃

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