臺灣博碩士論文加值系統

Bi2Te3系列化合物是室溫範圍下擁有極佳熱電優值的熱電材料，可作為廢熱回收系統與致冷元件的應用。本實驗採用粉末冶金成型之Bi0.5Sb1.5Te3（p型）半導體材料，透過熱擴散掺雜製程製備成特殊掺雜形式之熱電材料，其優異熱電優值表現值得持續研究。由於掺雜效應的影響，導致許多傳統熱電性質量測技術並不合適，故實驗重點設定在開發量測技術，並從量測結果推斷特殊掺雜熱電材料的性質表現。
本實驗測量已掺雜之熱電材料與未掺雜之熱電材料的基本性質，發現其載子濃度差異顯著。藉高解析電子微探儀分析掺雜元素之空間分佈，經由理論計算得其擴散方程式，
　 ，
與單晶Bi2Te3材料之擴散研究的文獻比較，本實驗所得之擴散係數（ ）與活化能（ ）介於平行c軸與垂直c軸的擴散結果之間。本實驗之擴散機制主要是藉由晶界與材料缺陷等高能量區域進行雜質擴散，故該結果屬合理值。最後，透過自行開發的掃描式四點探針量測技術，分析特殊掺雜熱電材料之電性表現隨位置分佈情形，可快速判定掺雜界面位置。

Abstract…………………………………………………………… I
摘要………………………………………………………………… II
誌謝………………………………………………………………… III
目錄………………………………………………………………… V
圖目錄……………………………………………………………… VIII
表目錄……………………………………………………………… XI
第一章、緒論…………………………………………………………………… 1
1.1　熱電效應……………………………………………… 2
1.1.1　Seebeck效應…………………………………… 2
1.1.2　Peltier效應…………………………………… 3
1.1.3　Thomson效應…………………………………… 4
1.2　熱電轉換效率………………………………………… 5
1.3　研究目的……………………………………………… 6
第二章、文獻回顧………………………………………………… 8
2.1　熱電材料傳輸理論…………………………………… 8
2.2　熱電材料發展的限制因素…………………………… 12
2.2.1　電子的電傳導與熱傳導……………………… 12
2.2.2　Seebeck效應與電子電傳導………………… 13
2.2.3　載子遷移率與載子有效質量………………… 13
2.2.4　聲子熱傳導與電子電傳導…………………… 14
2.3　Bi2Te3化合物半導體材料…………………………… 15
2.3.1　Bi2Te3晶體結構……………………………… 15
2.3.2　Bi2Te3內部缺陷……………………………… 17
2.3.3　Bi2Te3塊材製備方法…………………………18
2.4　熱電材料現狀………………………………………… 23
2.4.1　降低熱傳導係數……………………………… 24
2.4.2　掺雜微量元素………………………………… 25
2.4.3　熱電二極體（thermal diode）..………… 25
2.5　研究動機……………………………………………… 26
第三章、實驗設計……………………………………………… 28
3.1　實驗流程………………………………………………28
3.2　實驗步驟與原理……………………………………… 28
3.2.1　製備Bi-Sb-Te合金…………………………… 28
3.2.2　粉末冶金製程………………………………… 28
3.2.3　梯度掺雜製程………………………………… 30
3.2.4　性質量測與分析……………………………… 31
第四章、結果與討論…………………………………………… 35
4.1　製程改善與標準製程建立…………………………… 35
4.1.1　改善粉末冶金製程…………………………… 35
4.1.2　掺雜效應對Bi-Sb-Te材料熱電性質之影響…35
4.2　梯度型熱電材料之製程與性質………………………39
4.2.1　電流輔助退火製程………………………… 39
4.2.2　電流方向之影響…………………………… 41
4.2.3　電流輔助退火製程之問題與改善……………42
4.2.4　熱擴散退火製程…………………………… 44
4.3　熱擴散梯度掺雜分析……………………………… 47
4.3.1　掺雜濃度之空間分佈……………………… 47
4.3.2　熱擴散之掺雜濃度分析…………………… 48
4.4　梯度型Bi-Sb-Te熱電材料性質研究……………… 55
4.4.1　掃描式四點探針量測……………………… 55
4.4.2　ABST-BST掺雜界面的熱導性、電導性研究 57
4.4.3　掃描式Seebeck係數量測…………………… 60
4.4.4　掺雜界面深度檢測…………………………65
4.4.5　梯度型熱電材料之理論模型假設……………66
第五章、結論…………………………………………………… 68
參考文獻………………………………………………………… 70

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