今日的電子元件因為不斷的追求速度，致使元件操作溫度提高，然而高溫卻會嚴重損害電子元件的性能，對晶片設計者及製程工程師來說，更是一項亟待突破的問題，然而傳統的熱電元件因為具有較高
消耗功率及反應時間較慢等缺點，所以十分必要儘速研發出具備高整
合度及高效能的熱電元件已提供更優質的散熱能力。
本論文致力於研發一種以電化學技術沉積碲化鉍(Bi2Te3)、碲化銻
(Sb2Te3)熱電薄膜的方法，並且藉由設計一組可控制旋轉速率之電鍍
電極，以及可精密調變電流密度的電鍍設備，使得薄膜之熱電特性(例如電導率、熱導率以及Seebeck參數)達到最佳化，最後並結合微機電技術以開發出微熱電元件。
整個元件的製程首先是在矽晶圓上成長0.5µm的熱氧化層，之後
利用電子束蒸鍍機鍍上0.3µm的金與0.1µm的鉻以形成元件下電極部
份，其中金的微影製程是採用Lift-off製程來製版，接下來本論文採用7µm的厚光阻(AZ4620)作為電鑄模仁以分別進行Bi2Te3及Sb2Te3之電化學沉積，而元件的上電極部分仍是以電子束蒸鍍0.3µm金之後再用Lift-off製版，最後才利用鉻蝕刻液將下電極裸露之鉻金屬層去除以完成下電極的圖形定義。
本論文所設計的微熱電致冷元件之基本尺寸與佈局為：L 50µm x
W 50µm x H 5µm的Bi2Te3與Sb2Te3交錯式陣列柱狀體，並利用上下電極的連接得以形成多組PN熱電材料串接的元件結構，最後經量測顯
示元件在室溫下的ZT值可達到0.0088。

Today’s electronic components draw high levels of power and run at high temperature, which can present overheating problems for engineers and designers. They must find ways to keep the equipment cool or watch them fail prematurely. The conventional thermoelectric devices are high power consµming and slow response. We need more integrated and high performance thermoelectric device. Because of the
limit of material characteristics, the figure of art rising with the quality of epitaxial layer. We gave a cheaper and easier fabrication to realized this demand.
We present a micro thermoelectric device fabricated by Bi2Te3 electrochemical process. By using rotary cathode electrode, the current density can be well-proportioned. The thermal conduction and resistivity can be optimizing by this design. Also using the MEMS technology with repeated exposure and development of multiple photoresist layers, several different metals (Au, Cr) and thermoelectric
materials (Bi2Te3, Sb2Te3) are fabricated.
The SiO2 of 0.5µm was grown. Then the 0.3μm-thick Au on oxidized Si sputtered with a 1μm thick layer of Cr. And the bottom electrode was patterned by lift-off. Thick positive photoresist with one set of holes developed. Bi2Te3 was deposited by electrochemical deposition. And the Sb2Te3 is growing with the same method. The upper electrode sputtered with thin Au film and pattern by lift-off.
Finally, Cr was etched to electrically isolate the bottom interconnects.
The area of Bi2Te3 is about 50x50μm2. And it’s high about 5μm. The ZT value of Bi2Te3, which is measured and verified to be around 0.0088.

第一章熱電技術之介紹………………………………………………1
1-1 熱電技術與應用之發展…………………………………………1
1-1-1 熱電技術的演進……………………………………………1
1-1-2 熱電元件的應用……………………………………………4
1-2 熱電致冷器的發展…………………………………………………8
第二章微熱電致冷器的原理…………………………………………10
2-1 齊貝克效應（Seebeck Effect）………………………………10
2-2 帕耳帖效應（Peltier Effect）……………………………11
2-3 湯姆生效應（Thompson Effect）……………………………12
2-4 熱電模組( Thermoelectric Module) - Peltier Element…13
2-5 微熱電致冷器材料的選擇………………………………………21
第三章電化學沉積原理………………………………………………23
3-1 電極電位……………………………………………………………23
3-2 電化學沉積的物理過程與動力學…………………………………27
第四章微熱電元件設計與製作……………………………………30
4-1 ANSYS 有限元素分析熱電特性…………………………………30
4-2 微熱電元件製作流程圖…………………………………………34
4-3 微熱電元件製程模組說明………………………………………37
4-3-1 微熱電元件下電極部份…………………………………37
4-3-2 Bi2Te3及Sb2Te3熱電薄膜之電化學沉積參數測試……37
4-3-3 電化學沉積P N 熱電薄膜沉積與製版…………………44
4-3-4 熱電元件之上電極………………………………………47
第五章建議事項與討論………………………………………………50
Reference……………………………………………………………53

1. Da-Jeng Jeffrey Yao, “In-plane MEMS Thermoelectric Microcooler”, Ph. D. dissertation of UCLA , USA, (2001).

2. Mordechay Schlesinger “Modern Electroplating” 4th edition

3. Massoud Kaviany, “Principles of Heat Transfer”, John Wiley ＆ Sons,

4. 元智大學最佳化設計實驗室“機械設計教材－有限元素分析”

5. Marisol S. Martin-Gonzalez, Amy L. Prieto, Ronald Gronsky, Timothy Sands and Angelica M. Stacy “Insights into the Electrodeposition of Bi2Te3" Journal of the Electrochemical Society,2002

6. Gisberteimkuhler, Lngokerkamm, RolfReineke-koch
ical Society,2002

7. G.JEFFREY SNYDER,JAMES R. LIM,CHEN-KUO HUANG
JEAN-PIERRE FLEURIAL ”Thermoelectric microdevice fabricated by a MEMS-like electrochemical process” 2003, Nature

8. 林直慶， 微機電式熱電效應致冷器之設計與製作(Design and Fabrication of Thermo -electric Coolers Using MEMS Technology)”，清華大學電子所碩士論文，(2001).