本論文致力於N型碲化鉍(Bi2Te3)與P型碲化銻(Sb2Te3)熱電薄膜電化學沉積技術之建立並應用於微熱電致冷器(micro thermoelectric cooler, μ-TEC)之開發。本研究成功設計與建立一組可精密控制沉積電流與調變電極旋轉速率的熱電薄膜電鍍系統，並探討電流密度與退火參數對所沉積之熱電薄膜材料之電導率以及Seebeck係數的影響。另ㄧ方面，為了提高微熱電致冷器之元件散熱效益，本論文採用陣列交錯式排列之串聯式P/N型熱電薄膜柱狀體佈局設計。
本論文經實驗證明8-μm厚之碲化鉍(N型)熱電薄膜之Seebeck係數在最佳化條件下可達-86 μV/K，且功率因子為2.64×10-4 W/K2m；相同厚度之碲化銻(P型)熱電薄膜之Seebeck係數在最佳化條件下可達68 μV/K，且功率因子為1.41×10-4 W/K2m。在微熱電致冷器元件散熱效果方面，本論文所提之微熱電致冷器在5V之外加電壓下，其上下平面電極最大之溫差值可達1.3 °C，此值與國外相關研究中最具代表性之文獻 - Nature materials 2004 所顯示之2 °C致冷效果相差不大。

This paper presents an integrated column-type micro thermoelectric cooler (μ-TEC) constructed with serial connected p-type antimony-tellurium (Sb2Te3) and n-type bismuth-tellurium (Bi2Te3) micro pillars deposited by electrochemical deposited technology. To optimize the power factor, density and uniformity of the TE films and to enhance the reproducibility of μ-TEC device, a cathode with tunable rotary speed and
with accurate current controller has been designed in the electroplating system of this research.
The electroplating deposited Bi2Te3 and Sb2Te3 with an average thickness of 8 μm, are connected using Cr/Au layers at the hot junctions and cold junctions. The measured Seebeck coefficient and electrical
resistivity are -86 μV/K and 16 μΩ-m for Bi2Te3 films after annealed at 250°C, and are 68 μV/K and 30 μΩ-m for Sb2Te3 films after annealed at 200°C. The optimized power factors of the n-type (2.64×10-4 W/K2m) and p-type (2.64×10-4 W/K2m) telluride compounds have been demonstrated in this paper. Under 5 volts driven, the integrated μ-TEC device shows average cooling achieved is about 1.3 °C.

摘要............................................................................................................. I
Abstract ......................................................................................................II
誌謝...........................................................................................................III
目錄.......................................................................................................... IV
圖目錄..................................................................................................... VII
表目錄...................................................................................................... XI
第一章 緒論...............................................................................................1
1-1 研究背景........................................................................................1
1-2 文獻回顧.......................................................................................2
1-3 研究動機與目的..............................................................................7
1-4 研究流程與論文架構......................................................................9
第二章 原理分析.....................................................................................11
2-1 熱電效應........................................................................................11
2-1-1 Seebeck 效應............................................................................11
2-1-2 Peltier 效應..............................................................................14
2-1-3 熱電模組.................................................................................18
V
2-2 微熱電致冷器之效能影響因素....................................................20
2-3 化合物半導體熱電材料之選擇....................................................22
2-4 電化學沉積技術簡介.....................................................................23
2-5 熱電材料特性量測原理................................................................25
2-5-1 電阻率量測方法.....................................................................25
2-5-2 Seebeck 係數量測方法...........................................................27
2-5-3 微熱電致冷器之性能量測系統.............................................28
第三章 實驗方法與步驟.........................................................................30
3-1 電化學沉積碲化鉍與碲化銻熱電薄膜........................................30
3-2 微熱電致冷器光罩佈局之設計....................................................31
3-3 微熱電致冷器之元件製作.............................................................33
3-3-1 製作流程.................................................................................33
3-3-2 製作方法與製程參數.............................................................34
3-4 實驗設備規格................................................................................43
第四章 實驗結果與討論.........................................................................51
4-1 熱電薄膜特性量測與分析.............................................................51
4-1-1 碲化鉍與碲化銻熱電薄膜之表面微結構.............................51
4-1-2 碲化鉍與碲化銻熱電薄膜之組成分析.................................54
VI
4-1-3 碲化鉍與碲化銻熱電薄膜之Seebeck 係數量測與分析...............57
4-1-4 碲化鉍與碲化銻熱電薄膜之電阻率量測與分析.................58
4-1-5 碲化鉍與碲化銻熱電薄膜之功率因子分析.........................60
4-2 微熱電致冷器之性能量測與分析.................................................62
第五章 結論與未來展望.........................................................................70
5-1 結論................................................................................................70
5-2 建議................................................................................................72
參考文獻...................................................................................................73

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