本論文致力於發展平面式微型氯化銀參考電極之晶圓級封裝方法與電化學特性(包括電位穩定度與補償電位、交流阻抗、循環伏安曲線、電化學雜訊與再現性)之分析，以期能進一步結合各種生醫或生化微感測器而大幅縮減整個感測系統的尺寸，並提昇其成為商用化可攜式檢測產品的可能性。
本論文首度成功利用體型矽微加工技術、薄膜沈積與氯化技術完成全球最小尺寸(9 mm (L) × 6 mm (W) × 1 mm (H))之平面式微型氯化銀參考電極模組，整個模組包含兩個具不同功能且互相黏結的晶片。其中之一定義為「電極晶片」，該晶片表面沈積有Ti (60 nm)/Pd (60 nm)/Ag (4 µm)等三層薄膜，並透過氯化製程形成Ti/Pd/Ag/AgCl的平面式準參考電極結構。另一晶片稱為「封裝晶片」，該晶片具有兩個微矽蝕刻腔體結構：一個腔體可填充與密封1.33 ~ 6.40 μL的氯化鉀洋菜膠(KCl–agarose gel)以作為Ti/Pd/Ag/AgCl電極的鹽橋；另一腔體可作為放置外部導線與參考電極連接導電膠的用途。整個微型氯化銀參考電極模組經實驗證明具有相當優異的特性，包括：(i)長期電位穩定度極高：三萬秒下所量得電極電位之變化量低於4 mV；(ii)補償電位極低：最低可達0 mV；(iii)交流阻抗1~ 20 KΩ；(iv)經循環伏安法證明可得到穩定CV曲線；(v)電化學雜訊低；(vi)電極之再現性很高(三萬秒電位漂移量= 3 ~ 8 mV；補償電位範圍= -6 ~ 3 mV)。
綜觀以上諸多優良電化學特性，本論文所設計製作之微型氯化銀參考電極與商用參考電極相比毫不遜色，然而利用微機電系統技術卻可使其體積大幅縮小250倍，這是本文最重要的貢獻所在。

This thesis devotes to develop a wafer-level packaging technique of the planar AgCl-based micro reference electrode and to investigate its various electrochemical characteristics (including the potential stability and offset voltage, AC impedance, cyclic-voltammetry analysis, electrochemical noise and reproducibility). The miniaturized all-solid-state reference electrode can integrated with many biomedical or biochemical sensors for substantially reduce the dimension of the whole sensing system and improve the commercial capability of portable detecting products.
This study reports firstly a smallest module of the micro reference electrode with dimension only about 9 mm (L) × 6 mm (W) × 1 mm (H) in the worldwide using the silicon bulk-micromachining technology, thin film deposition and chloridation techniques. The packaged reference electrode module is constructed by two bonded wafers with different functions. One wafer of this module is defined as “electrode chip” and it has a Ti/Pd/Ag/AgCl planar quasi-reference electrode deposited on its surface. Another wafer is called as “packaging chip” and it has two bulk-micromachined silicon cavities for the filling/sealing of 1.33 ~ 6.40 μL KCl-gel (as the salt-bridge of electrode) and electrical connection. Many electrochemical characteristics of the encapsulated solid-state micro reference electrode are tested and improved for the commercial applications. Including a very stable cell potential (<4 mV in 30000 sec.), an approximately zero offset-voltage, a low AC impedance (1~20 KΩ), and high reproducibility (drift less than 3~8 mV in 30000 sec. and the range of offset voltage is -6 ~ 3 mV) of the packaged micro reference electrode are demonstrated. Furthermore, stable CV curve of the packaged Ti/Pd/Ag/AgCl/KCl-gel reference electrode were proved by cyclic-voltammetry analysis and its low electrochemical noise spectrum was investigated and discussed in this work.
Compared with the commercial reference electrode, the planar miniaturized AgCl reference electrode module developed in this thesis has displayed its many excellent characteristics and with a dimension only 250 times smaller than the conventional reference electrode.

致謝……………………………………………………………..I
中文摘要………………………………………………………II
英文摘要………………………………………………………III
目錄……………………………………………………………V
圖目錄………………………………………………………VII
表目錄…………………………………………………………X

第一章 緒論
1-1 參考電極簡介……………………………………………1
1-2 論文研究動機……………………………………………3
第二章 參考電極之電化學特性介紹
2-1 電位穩定度及補償電位……………..………………….....5
2-1-1 可逆電極反應………………………………………..5
2-1-2 質量傳遞……………………………………………. 6
2-2 線性掃描伏安法和循環伏安法…………….…………..…7
2-3 交&#63946;阻抗分析………………………………………………9
2-3-1 電解池等效電路……………………………………11
2-3-2 擴散阻抗…………………………………………14
2-3-3 擬電路元件之物理電化學性質…………………17
2-4 電化學雜訊分析…………………………………………19
第三章 平面式微型氯化銀參考電極模組之設計、製作與封裝
3-1 Ti/Pd/Ag/AgCl電極晶片的設計與製作…………………21
3-2 KCl-gel封裝晶片的設計與製作………………………23
3-3 平面式微型氯化銀參考電極模組之封裝與電性連接…30
3-4 實驗設備規格與製程參數………………………………32
3-4-1 交大奈米中心實驗室設備…………………………32
3-4-2 清大奈米中心實驗室設備…………………………33
3-4-3 南區國家奈米元件實驗室設備（NDL）……………34
3-4-4 中山大學奈米微系統實驗室設備…………………41
3-4-5 日月光半導體封裝設備……………………………42
3-5 實驗藥品規格……………………………………………44
第四章 電化學分析與特性改善
4-1 電位穩定度與補償電位…………………………………45
4-2 交流阻抗分析……………………………………………51
4-3 循環伏安曲線……………………………………………54
4-4 電化學雜訊分析…………………………………………61
4-5 再現性……………………………………………………63
第五章 結論與對未來展望
5-1 結論………………………………………………………64
5-2 對未來展望………………………………………………65
參考文獻………………………………………………………66

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