热电材料高通量实验制备与表征方法

doi:10.15541/jim20180335

摘要/Abstract

摘要：

高通量材料实验旨在利用较少的实验次数快速获得成分-物相-结构-性能之间关系, 筛选出组分最优的材料体系, 目前已在超导材料、荧光材料以及巨磁阻材料等方面有较多应用。热电材料是可以实现热能和电能直接相互转换的功能材料, 在温差发电和废热利用等领域有着重要的应用价值, 但热电材料的传统实验制备与表征方法存在着实验周期长和效率低等问题。因此, 将高通量实验的方法和理念引入新型热电材料的研发和优化具有重要的理论和实际意义。本文主要总结和梳理了现有在热电材料实验研究中具有较好应用前景的高通量实验制备与表征技术, 包括高通量样品制备、成分-结构高通量表征、电-热输运性能高通量表征等, 并分析了各高通量实验技术在实验热电材料研究中的优势和局限性, 希望为今后热电材料高通量实验优化和筛选提供一定的参考。

关键词: 高通量实验, 热电材料, 电输运性能, 热导率, 综述

Abstract:

High-throughput experiments aimed to promptly obtain the relationship among composition-phase-structure-performance with fewer experiments and screen out optimal material systems with optimized compositions. Up to now, high-throughput experiments are successfully applied in superconducting materials, fluorescent materials and giant magnetoresistance materials. Thermoelectric materials are functional materials that can realize the direct conversion between thermal energy and electrical energy and can be potentially applied in the fields of thermoelectric power generation and waste heat utilization. However, traditional preparation and characterization methods for thermoelectric materials have disadvantages of time consuming and low efficiency. Therefore, it is of great theoretical and practical significance to introduce methods and concepts of high-throughput experiments into development and optimization of new thermoelectric materials. In this paper, we summarize and discuss the existing high-throughput experimental preparation and characterization techniques with great application prospects in thermoelectric materials, including high-throughput sample preparation, composition-structure, and electro-thermal transport properties characterization, and then analyze the advantages and limitations of these high-throughput techniques. We hope to provide a reference for future high-throughput optimization and screening of thermoelectric materials.

Key words: high-throughput experiement, thermoelectric materials, electrical transport properties, thermal conductivity, review

中图分类号:

TB34

骆军, 何世洋, 李志立, 李永博, 王风, 张继业. 热电材料高通量实验制备与表征方法[J]. 无机材料学报, 2019, 34(3): 247-259.

LUO Jun, HE Shi-Yang, LI Zhi-Li, LI Yong-Bo, WANG Feng, ZHANG Ji-Ye. Progress on High-throughput Synthesis and Characterization Methods for Thermoelectric Materials[J]. Journal of Inorganic Materials, 2019, 34(3): 247-259.

图/表 22

图1 128种二元材料库[15]

Fig.1 A 128-member binary library[15]

图2 “M-ist Combi”组合静电雾化系统原理图[16]

Fig.2 Schematic diagram of combinatorial electrostatic atomization system “M-ist Combi”[16]

图3 切克劳斯基晶体生长示意图[18]

Fig. 3 Schematic illustration for the Czochralski crystal growth[18]

图4 布里奇曼晶体生长法示意图[19]

Fig.4 Schematic illustration for the vertical Bridgman crystal growth[19]

图5 n-型0.01/0.055% PbI2掺杂的(Pb0.95Sn0.05Te)0.92(PbS)0.08功能梯度材料塞贝克系数分布[24]

Fig.5 Variation of Seebeck coefﬁcient values along n-type 0.01/0.055% PbI2 doped (Pb0.95Sn0.05Te)0.92(PbS)0.08 functionally graded materials[24]

图6 (a)高温超速离心机示意图和(b)离心过程原子再分布原理示意图[25]

Fig.6 (a) Scheme of a rotor with capsules for sedimentation experiment and (b) mechanism of sedimentation of atoms in the strong acceleration field[25]

图7 (a)退火后的Ti-Ni-Sn薄膜材料库照片和(b~d)以颜色编码的材料库高通量成分EDX表征结果[27]

Fig.7 (a) Optical image of the annealed Ti-Ni-Sn thin film materials library; (b-d) color-coded results of the high-throughput EDX measurements of the material library[27]

图8 EDX表征的Mg\Ni\Al元素分布图[30]

Fig.8 EDX measurements of the concentration of (a)magnesium, (b)nickel and (c)aluminum of an Mg-Ni-Al ternary thin film library[30]

图9 单个量热器结构示意图[34]

Fig.9 Layout of the nanocalorimeter cell[34]

图10 (a)Cu/Si元素比例、(b)玻璃态转化温度/℃和(c)玻璃化转变总焓[35]

Fig.10 Composition trends over the sample library, (a) Si:Cu ratio for the glass-forming component, (b) glass transition temperature and (c) the total enthalpy of this glass reaction[35]

图11 (a)泵浦和探测激光探测装置原理图以及(b)样品表面温度与时间关系[33]

Fig.11 (a) Schematic of the pump and probe laser measurement setup and (b)temperature increase as a function of time after a single-pulse[33]

图12 TDTR实验装置示意图[33]

Fig.12 Time-domain thermoreflectance experimental setup[33]

图13 (a)Cr-Ti扩散节热导分布图和(b)热导率变化数值(图(a)中虚线)[40]

Fig.13 (a)Thermal conductivity imaging of a Cr-Ti diffusion couple and (b) numerical values for thermal conductivity across the path shown as a dashed line in (a)[40]

图14 SThM装置示意图[43]

Fig.14 Schematic illustration of SThM setup[43]

图15 (a)由不同导热率的样品引起的探针电阻的变化, (b)样品电阻分布图, (c) Yb0.7Co4Sb12中相应的热导率, (d)不同微区之间的界面上的电阻变化的实际线扫描与模拟值[45]

Fig. 15 Quantitative mapping of thermal conductivities, (a) changes in the probe resistance induced by samples with different thermal conductivities; Mappings of (b) resistance change and (c) corresponding thermal conductivities in Yb0.7Co4Sb12; (d) Line scan of resistance change across an interface between different phases[45]

图16 由SThM获得的相同区域的Ag2Se薄膜(a) SEM形貌, (b) AFM形貌图和(c)热成像图[46]

Fig.16 (a) SEM image, (b) AFM topography image, and (c) thermal map image obtained with the SThM technique are shown simultaneously for the same area of the Ag2Se thin film[46]

图17 高温热电塞贝克系数探针的实物图[14]

Fig.17 A photograph of the high temperature thermoelectric power factor screening tool and the Seebeck coefﬁcient probe[14]

图18 PSM装置示意图[48]

Fig.18 Schematics of PSM setup[48]

图19 (a)硅/金基底和(b)石英/金基底时不同厚度的Bi2Te3薄膜塞贝克系数映像[49]

Fig.19 Thermopower mappings with different thicknesses grown on Si/Au(a)and quartz/Au(b) substrates[49]

图20 Bi2Te2Se基梯度材料的塞贝克系数分布[50]

Fig.20 Seebeck coefficient distribution of the Bi2Te2Se sample with composition gradient[50]

图21 AFM加热探针技术表征塞贝克系数的示意图[52]

Fig.21 Schematic diagram of the AFM conductive, heated probe technique for nanoscale Seebeck coefficient characterization[52]

图22 (a) Bi2Te3的AFM形貌图和(b)塞贝克系数的三维柱状图, 对应于a中的49个位置[52]

Fig.22 (a) AFM topography image of Bi2Te3 thin film with 49 locations for nanoscale and (b) Seebeck voltage measurement, as indication by 49 dots in (a)[52]

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