臺灣博碩士論文加值系統

CoSb3是有高zT值的熱電材料，近幾年內有許多文獻研究如何增加此材料的效率，其中包括在Co或Sb的位置摻雜原子以及在材料中加入原子填充，這兩種方法都能大幅的提升CoSb3材料的zT值。目前n-type的CoSb3研究已經相當成熟，但是對於熱電元件而言，p-type的CoSb3研究也是相當重要，文獻中尚未有人研究: 利用化學還原法製備p-type CoSb3摻雜Fe並引入In填充是否能進一步增加CoSb3熱電性質。研究顯示Fe摻雜可以使CoSb3變為p-type，而透過填充原子在CoSb3的晶體結構中有助於降低晶格熱導。這篇文章對CoSb3摻雜Fe並引入In填充進行研究，研究主要有三個結果，第一: 利用化學還原法成功製備出p-type的Fe-doped CoSb3，並找到摻雜的極限，接著利用熱壓的方式提升導電度。第二: 利用不同製程去比較其熱電性質，發現製程二製備出的粒徑較小，使得熱導度比製程一還低。第三: 將製程一和二摻雜Fe中最好的樣品用gas-solid reaction進行In填充，結果發現In填充能夠進一步再降低熱導度，讓熱電優值上升。因此摻雜Fe加In填充這個方法真的能進一步提升CoSb3材料的zT值，而且是用新的方法來製備CoSb3樣品。所有樣品中，製程一摻雜Fe及In填充的In0.7Co3Fe1Sb12 擁有最好的zT值:0.40。

The zT value of CoSb3 system is high among thermoelectric materials. For the recent years, many research works focus on how to further improve zT value of this material including doping atoms and filling atoms. Nevertheless, no research works consider on using chemical reduction to prepare the p-type Fe-doped CoSb3 and introducing of In-filled to enhance the zT value, In this study, doping iron and introducing Indium-filled simultaneously in CoSb3 system is applied to produce three main results. First, the p-type Fe-doped CoSb3 was successfully prepared by chemical reduction method, and found the doping limit of Fe. Second, Using different processes to compare the thermoelectric propoties. Third, the sample with the highest zT value in the process of the first and second,filling Indium by gas-solid reaction.It was found that Indium-filled can further reduce the thermal conductivity and increase the thermoelectric figure of merit. As the results, doping iron and introducing Indium-filled simultaneously in CoSb3 really improves the zT value. Among all samples, In0.7Co3Fe1Sb12, which means doping iron 25% and introducing Indium-filled in CoSb3 system, has the highest zT value of 0.40.

摘要 I
Abstract II
目錄 III
圖目錄 IV
表目錄 VIII
第一章 簡介 1
1.1前言 (熱電效應、判斷材料好壞、應用方面) 1
1.2 研究動機 (為何選擇熱電材料、為何選擇CoSb3、摻雜加填充、化學還原法製程) 12
1.3 CoSb3材料介紹 (結構及特性、CoSb3已摻雜過之元素概覽、近年p-type CoSb3傑出研究、zT值) 15
第二章 實驗原理 20
2.1製程的優缺點(化學還原法、固態燒結法) 20
2.2 X光繞射 (X光的歷史、x光如何產生、x光濾片、X光訊號偵測、晶體描述方式、布拉格繞射、影響繞射峰強度的因子) 21
2.3電阻率(Resistivity) 44
2.4熱電力(Thermopower or Seebeck coefficient) 48
2.5熱導度(Thermal Conductivity) 50
2.6霍爾效應 52
2.7 密度(Density) 55
2.8掃描式電子顯微鏡(Scanning Electron Microscope) 56
2.9 SPB model 材料參數分析 58
2.10 EPMA電子微探儀 62
第三章 實驗製程及實驗儀器 63
3.1實驗製程(Fe摻雜、Fe摻雜及In填充) 63
3.2實驗儀器 68
第四章 實驗結果與分析 78
4.1 製程一之Co4-xFexSb12 (x=0、0.6、0.8、1.0、1.2) 78
4.2製程二之Co4-xFexSb12 (x=1.0、1.2、1.4) 103
4.3摻雜Fe及In填充對CoSb3熱電性質的影響 125
第五章 討論與結論 139
參考文獻 143

[1] Wikitechy School, “Thomsons Effect Effect of electric current class 12 physics
subject notes letures”,
https://www.youtube.com/watch?v=N88S9eTjoJ0 (2016).
[2] wiki, “Thermoelectric effect”, https://en.wikipedia.org/wiki/Thermoelectric_effect
(2018).
[3] Gangjian Tan, Li-Dong Zhao, and Mercouri G. Kanatzidis, “Rationally Designing
High-Performance Bulk ThermoelectricMaterails”, Chem.Rev., 116(19),
pp.123123-12149 (2016).
[4] wiki, “Voyagar 1”,
https://zh.wikipedia.org/wiki/%E6%97%85%E8%A1%8C%E8%80%851%E5%8F%B7 (2013).
[5] Viktor Karlsson, “Thermoelectric Cooler Prototype Based on Bismuth Telluride
and Aimed for Space Applications”, UPTEC Q, ISSN 1401-5773(2017)
[6] J. O. Sofo, G. D. Mahan, “Electronic structure of CoSb3:A narrow-band-gap semiconductor”, PHYSICAL REVIEW B, 58, pp. 15620-15623 (1998)
[7] Yongkwan Dong,Pooja Puneet,Terry M. Tritt,George S. Nolas, “Crystal structure and high temperature transport properties of Yb-filled p-type skutterudites YbxCo2.5Fe1.5Sb12”,Journal of Solid State Chemistry 209,pp.1-5 (2014)
[8] Nusrat Shaheen,Xingchen Shen,Muhammad Sufyan Javed,Lijie Guo,Aijuan
Zhang,Xu Lu,Guoyu Wang,Xiaoyuan Zhou,“Super-fast preparation of Nd-filled p-type skutterudite compounds with enhanced thermoelectric propeties”,Ceramics International,43,pp.7443-7447 (2017)
[9] Jesus Prado-Gonjal,Paz Vaqueiro,Chris Nuttall,Robert Potter,Anthony V.Powell,
“Enhancing the thermoelectric properties of single and double filled p-type skutterudites synthesized by an up-scaled ball-milling process”,Journal of Alloys and Compounds,695,pp.3598-3604 (2017)
[10] Jian Yu,Wenyu Zhao,Hongyu Zhou,Ping Wei and Qingjie Zhang, “Rapid preparation and thermoelectric properties of Ba and In double-filled p-type skutterudite bulk materials”,Scripta Materialia,68,pp.643-646 (2013)
[11] Tulashi Dahal,Hee Seok Kim,Sonika Gahlawat,Keshab Dahal,Qing Jie,Weishu Liu,Yucheng Lan,Kenneth White,Zhifeng Ren,“Transport and mechanical properties of the double-filled p-type skutterudites La0.68Ce0.22Fe4-xCoxSb12”,Acta Materialia,117,pp.13-22 (2016)
[12] Chen Zhou,Donald Morelli,Xiaoyuan Zhou,Guoyu Wang,Ctirad Uher,
“Thermoelectric properties of p-type Yb-filled skutterudite YbxFeyCo4-ySb12”,
Intermetallics, 19, pp.1390-1393 (2011)
[13] Soon-Chul Ur, Joon-Chul Kwon, IlHo Kim, “Thermoelectric properties of Fe-doped CoSb3 prepared by mechanical alloying and vacuum hot pressing”, Journal of Alloys and Compounds, 442, pp.358-361 (2007)
[14] KWAN-HO PARK, JAE-YONG JUNG, SOON-CHUL UR, and IL-HO KIM, “Synthesis and Thermoelectric Properties of InzCo4-xFexSb12 Skutterudites, Journal of ELECTRONIC MATERIALS”, 39, pp.1750-1754 (2010)
[15] Mohsen Yakshi Tafti, Mohsin Saleemi, Muhammet S. Toprak et al., “Fabrication and characterization of nanostructured thermoelectric FexCo1-xSb3”, Open Chem., 13, pp.629-635 (2015)
[16] Yadi Liu, Xiaohui Li, Qian Zhang et al., “High pressure synthesis of p-type Fe-substituted CoSb3 skutterudites”, J Mater Sci: Mater Electron, 27, pp.6433-6437 (2016)
[17] Jiangying Peng, Junyou Yang, Tongjun Zhang et al., “Preparation and characterization of Fe substituted CoSb3 skutterudite by mechanical alloying and annealing”, Journal of Alloys and Compounds, 381, pp.313-316 (2004)
[18] Kwan-Ho Park, Soon-Chul Ur and ll-Ho Kim, “Thermoelectric Properties of Co1-xFexSb3 Prepared by Encapsulated Induction Melting”, Solid State Phenomena, 124-126, pp.939-942 (2007)
[19] ll-Ho Kim, Soon-Chul Ur, “Electronic transport properties of Fe-doped CoSb3 prepared by encapsulated induction melting”, Materials Letters, 61, pp.2446-2450 (2007)
[20] Kwan-Ho Park, Jung-ll Lee, Soon-Chul Ur and ll-Ho Kim, “Thermoelectric Properties of Fe-doped CoSb3 Prepared by Encapsulated Induction Melting and Hot Pressing”, Materials Science Forum, 534-536, pp.1557-1560 (2007)
[21] J. Epp, “X-ray diffraction (XRD) techniques for materials characterization”, Foundation Institute of Materials Science, Bremen,Germany
[22] Virendra Singh*,H.M. Agrawal, “Qualitative soil mineral analysis by EDXRF XRD and AAS probes”, Radiation Physics and Chemistry, 81, pp.1796-1803 (2012)
[23] J.M.Zuo, “New method of Bravais lattice determination”, Ultramicroscopy, 52, pp.459-464 (1993)
[24] Maren Kahle,Markus Kleber,Reinhold Jahn, “Review of XRD-based quantitative analyses of clay minerals in soil: the suitability of mineral intensity factors”, Geoderma, 109, pp.191-205 (2002)
[25] PENG Jiangying, YANG Junyou, SONG Xinli et al., “Synthesis of Fe-substituted CoSb3-based skutterudite Co4-xFexSb12 by mechanical alloying-hot pressing-annealing”, Front.Mater.Sci.China,1(2), pp.177-180 (2007)
[26] Hiroaki Anno and Kakuei Matsubara, “Effects of Doping on Electronic Structure and Thermoelectric Properties of CoSb3”, J.Japan Inst.Metalsm, 63, pp.1407-1411 (1999)
[27] R.C. Mallik, R. Anbalagan, G. Rogl et al., “Thermoelectric properties of Fe0.2Co3.8Sb12-xTex skutterudites”, Acta Materialia, 61, pp.6698-6711 (2013)
[28] Degand Zhao, Changwen Tian, Yunteng Liu et al., “High temperature sublimation behavior of antimony in CoSb3 thermoelectric material during thermal duration test”, Journal of Alloys and Compounds, 509, pp.3166-3171 (2011)