臺灣博碩士論文加值系統

摘要

本實驗利用晶體熔融淬火和粉末冶金之冷壓燒結，製備三元合金化合物碲鉍化鉛(PbTe)n(Bi2Te3)m系列熱電材料，其中n：m =1：1，1：2，和2：1。同時使用EPMA，DSC，XRD和SEM來鑑定晶體結構及材料品質。在室溫中，所有試片呈現出高濃度的載子濃度分佈，其範圍在7.81×1019∼4.27×1020 (1/cm3)。試片之Seebeck係數，電阻率和熱傳導係數隨溫度變化的量測在300至600K之間進行。所有試片皆為n型傳導。在500K至600K溫度範圍有較高的ZT值，最佳的ZT值發生在550K時，大約是0.13。本論文將詳細討論碲鉍化鉛(PbTe)n(Bi2Te3)m系列晶體之熱電性質溫度和粉末粒度大小成分的關係。

Abstract

Polycrystalline samples of stoichiometric ternary compounds (PbTe)n(Bi2Te3)m , in which n：m = 1：1, 1：2 , 2：1 , have been prepared by melting and quenching followed by cold pressing. All the samples were investigated by electron probe microanalysis (EPMA), differential scanning calorimeter (DSC), X-ray diffraction analysis, scanning electron microscopy (SEM) for quality and crystal structures . At room temperature all the samples exhibit a high carrier concentration in the range 7.81×1019∼4.27×1020 (1/cm3).The temperature dependence of the Seebeck coefficient, resistivity and thermal conductivity of (PbTe)n(Bi2Te3)m samples were observed at temperature ranging from 300K to 600K. All compounds possess n-type of conductivity. The higher thermoelectric figures of merit (ZT) of samples were obtained between 500K and 600K and a maximum of about 0.13 was obtained at a temperature of 550K. The powder particle size and temperature dependence of the thermoelectric properties for (PbTe)n(Bi2Te3)m samples were discussed.

目錄

誌謝………………………………………………………………………....…i
摘要…………………………………………...………………………………ii
英文摘要………………………………………………………….…….……iii
目錄………………………………………………..………..….………….…iv
表目錄………………………………………………..………………...……vii
圖目錄…………………………………………………………...…….…......ix

一、前言………………………………………………………………………1
二、研究背景與文獻回顧…………………………….………………………5
2.1熱電現象…………………….……………………………………………5
2.2 ZT值…..………………………………………….……………………..10
2.3熱電材料的分類與應用…………………………..…………………….11
2.4成長方法………………………………………….………………….….13
　 2.4.1 Bridgman Method…...………….…………………………….…...13
　 2.4.2粉末冶金..…..………………….………………..…………….…..15
2.5 nPbTe-mBi2Te3系列熱電材料……………………………..……………16
　 2.5.1晶體結構與化學鍵結……………………………………………...16
2.6研究方向…………………………………………...……………………22
三、實驗方法…..…..………………………………………..……………….24
3.1實驗流程…………………………………….……………..…………….24
3.2粉末製備.…………….…………………….…………………………….25
3.3冷壓燒結………………………………..………………….….…………28
3.4特性量測分析…………………………………………….….…………..30
3.5特性量測原理與方法……………………………………..….………….30
　 3.5.1熱傳導係數與Seebeck係數量測原理與方法....…………………31
　 3.5.2電阻率量測…………………………………………….….……….35
　 3.5.3霍爾係數量測……………………………………………………...37
　 3.5.3.1霍爾效應之理論…………………………………………………37
　 3.5.3.2霍爾效應之量測方式……………………………………………39
四、實驗結果與討論………………………………………………………...42
4.1晶體淬火與粉末燒結結果分析…………………………………………42
　 4.1.1粉末粒度分佈結果分析………………….………………………..42
　 4.1.2 DSC分析結果……………………………………………………..45
　 4.1.3電子顯微分析結果………………………………………………...49
　 4.1.4 EPMA分析結果…………………………………………………..54
　 4.1.5 X-ray繞射分析結果………………………………………………57


4.2特性量測分析……………………………………………………………62
　 4.2.1電阻率……………………………………………………………...62
　 4.2.2 Seebeck係數………………………………………………………64
　 4.2.3熱傳導係數………………………………………………………...66
　 4.2.4霍爾係數與載子濃度……………………………………………...68
4.3綜合討論…………………………………………………………………85
五、結論……………………………………………………………………...89
參考文獻..……………………………………………….………..…………92

表目錄

表1.1、熱電性質之歷史回顧……………………………………………….4
表2.1、熱電材料在各方面的應用………………………………………….12
表2.2 PbBi4Te7、PbBi2Te4、Pb2Bi2Te5基本特性…………….………………20
表2.3、熱電產生器轉換效率一覽表………..….………………………….20
表3.1 PbBi4Te7、PbBi2Te4、Pb2Bi2Te5元素配重表………………...………..26
表3.2、篩網規格與粉體粒度分佈表……..….……………………..……….27
表3.3 PbBi4Te7、PbBi2Te4、Pb2Bi2Te5試片燒結溫度一覽表……………….28
表4.1 PbBi4Te7燒結後試片EPMA 定量結果…………………………..…54
表4.2 PbBi2Te4燒結後試片EPMA 定量結果……………………………..55
表4.3 Pb2Bi2Te5燒結後試片EPMA 定量結果…………………………….55
表4.4 PbBi4Te7、PbBi2Te4、Pb2Bi2Te5之XRD分析結果………………...58
表4.5 PbBi4Te7粉末經不同溫度與不同粒度燒結試片之電阻率一覽表…70
表4.6 PbBi2Te4粉末經不同溫度與不同粒度燒結試片之電阻率一覽表…72
表4.7 Pb2Bi2Te5粉末經不同溫度與不同粒度燒結試片之電阻率一覽表..73
表4.8 PbBi4Te7 粉末經不同溫度與不同粒度燒結試片之Seebeck係數
一覽表 ..…………………………………………………………………….75


表4.9 PbBi2Te4 粉末經不同溫度與不同粒度燒結試片之Seebeck係數
一覽表 ………………..…………………………………………………….77
表4.10 Pb2Bi2Te5 粉末經不同溫度與不同粒度燒結試片之Seebeck係數
一覽表 ……………………………………………………………………...78
表4.11 PbBi4Te7 粉末經不同溫度與不同粒度燒結試片之熱導一覽表…80
表4.12 PbBi2Te4 粉末經不同溫度與不同粒度燒結試片之熱導一覽表…82
表4.13 Pb2Bi2Te5粉末經不同溫度與不同粒度燒結試片之熱導一覽表....83
表4.14 PbBi4Te7、PbBi2Te4、Pb2Bi2Te5粉末經不同溫度與不同粒度燒結試片之霍爾係數與載子濃度一覽表 ....…………………………………..….84




















圖目錄

圖1.1、熱電冷卻器及熱電產生器簡圖…...…………………………………4
圖1.2、熱電致冷器基本結構圖………….…………………………………4
圖2.1、熱電偶產生相對Seebeck電動勢示意圖……..……………………7
圖2.2、Seebeck原理示意圖………………………………………………….8
圖2.3、Peltier效應熱電偶示意圖…………………………….…………….9
圖2.4、(a)在開放迴路單一導體的對稱性溫度梯度。(b)在封閉迴路單一導體中由Thomson效應產生的非對稱性溫度梯度………………………..…9
圖2.5、各種材料溫度對Z值的表現……………………………..…………12
圖2.6、Bridgman Method 晶體成長示意圖…………………….…………14
圖2.7、Bi2Te3化合物的晶體結構…………………………………………...19
圖2.8 (a) (b)、Pb-Bi-Te三元合金………………………………..…………20
圖3.1、實驗流程圖………………………………………………..………..24
圖3.2、真空封管示意圖……………………………………………………27
圖3.4、冷壓燒結程序圖…………………….……………………….….…29
圖3.5、比較法示意圖..……………………………………………….……31
圖3.6、Seebeck 係數量測系統圖…………………………………….……32
圖3.7、量測試片實體和示意圖……………..……………………….……33
圖3.8、熱傳導係數和Seebeck係數量測系統示意圖……………….……33
圖3.9、不規則形狀試片的四個接點……………………………………..…36
圖3.10、修正因子F對Rr的作圖…..………………………………………36
圖3.11、p-type的霍爾效應圖示……………………………………………37
圖3.12、霍爾量測試片接線示意圖………………………………………..41
圖3.13、儀器裝置示意圖…………………………………………………..41
圖4.1、元素熔融後經淬火所得之碲鉍化鉛晶體…………………………43
圖4.2、PbBi4Te7不同粉體粒度經燒結後所得試片外觀………………….43
圖4.3、PbBi4Te7依序經由(a)325、(b)200、(c)120、(d)70mesh篩網過篩後粉體粒度分佈圖 ..………………………………………………………….44
圖4.4、PbBi4Te7 試片DSC分析資料…………………………………….46
圖4.5、PbBi2Te4 試片DSC分析資料…………………………………….47
圖4.6、Pb2Bi2Te5 試片DSC分析資料……………………………………48
圖4.7、PbBi4Te7 粉體粒度44μm經由480℃燒結後(a)表面與(b)橫截面型態 ………………………………………………………………………...50
圖4.8、PbBi4Te7不同粒度經由380℃燒結後(a)表面與(b)橫截面型態..…51
圖4.9、(a) (b) PbBi2Te4經不同溫度燒結後(a)表面與(b)橫截面型態….…52
圖4.10、PbBi4Te7、PbBi2Te4、Pb2Bi2Te5晶體淬火後顯微組織與EPMA
定性分析 …………………………………………………………………...56
圖4.11、淬火後PbBi4Te7晶體與粉末及燒結後之x-ray比較圖…………...58
圖4.12、淬火後PbBi2Te4晶體與粉末及燒結後之x-ray比較圖……..…….59
圖4.13、淬火後Pb2Bi2Te5晶體與粉末及燒結後之x-ray比較圖…..……...59
圖4.14、PbBi4Te7粉末經不同溫度燒結後之x-ray比較圖………………...60
圖4.15、PbBi2Te4粉末經不同溫度燒結後之x-ray比較圖………………...60
圖4.16、Pb2Bi2Te5粉末經不同燒結溫度後之x-ray比較圖………………..61
圖4.17、PbBi4Te7粉末經不同溫度燒結試片之電阻率與溫度關係圖….…69
圖4.18、PbBi4Te7粉末經不同粒度燒結試片之電阻率與溫度關係圖…….69
圖4.19、PbBi2Te4粉末經不同溫度燒結試片之電阻率與溫度關係圖…….71
圖4.20、PbBi2Te4粉末經不同粒度燒結試片之電阻率與溫度關係圖…….71
圖4.21、Pb2Bi2Te5粉末經不同溫度燒結試片之電阻率與溫度關係圖.…..73
圖4.22、PbBi4Te7粉末經不同溫度燒結試片之Seebeck係數
與溫度關係圖……………………………………………………………….74
圖4.23、PbBi4Te7粉末經不同粒度燒結試片之Seebeck係數
與溫度關係圖……………………………………………………………….74
圖4.24、PbBi2Te4粉末經不同溫度燒結試片之Seebeck係數
與溫度關係圖……………………………………………………………….76
圖4.25、PbBi2Te4粉末經不同粒度燒結試片之Seebeck係數
與溫度關係圖……………………………………………………………….76


圖4.26、Pb2Bi2Te5 粉末經不同溫度燒結試片之Seebeck係數
與溫度關係圖..……………………………………………..……………….78
圖4.27、PbBi4Te7粉末經不同溫度燒結試片之熱導係數與溫度關係圖….79
圖4.28、PbBi4Te7粉末經不同粒度燒結試片之熱導係數與溫度關係圖….79
圖4.29、PbBi2Te4粉末經不同溫度燒結試片之熱導係數與溫度關係圖….81
圖4.30、PbBi2Te4粉末經不同粒度燒結試片之熱導係數與溫度關係圖….81
圖4.31、Pb2Bi2Te5粉末經不同溫度燒結試片之熱導係數與溫度關係圖...83
圖4.32、PbBi4Te7、PbBi2Te4、Pb2Bi2Te5各組成之ZT值……………………88
圖4.33、PbBi4Te7、PbBi2Te4、Pb2Bi2Te5各組成之power factor……………..88

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