電鍍銅技術廣泛運用在製造商用銅箔、銅複合板，以及半導體產業。透過調整電鍍參數，我們能夠生產不同特性的銅材以適應多樣的需求。近年來，多項研究發現，具有奈米雙晶結構的銅，其機械性能、抗氧化性質與催化性質皆有大幅地提升，且能有效改善電遷移現象。一般業界常使用脈衝電鍍的方式來製備雙晶，但該方法耗時，因此，本研究旨在探討使用較迅速的直流電鍍，根據不同電鍍液參數，以製備不同晶相優選的銅箔，並研究其中誘發雙晶生成的機制，因為相對於脈衝電鍍，直流電鍍的雙晶生成機制尚未有完整且直接的解釋。本論文研究主要包含兩大方向：
1.透過調整電鍍添加劑的比例和電流密度，製備不同優選晶面的銅箔。
首先，我們成功使用不同比例的明膠和氯離子，製備出(111)雙晶、(200)兩種優選晶面的銅箔。然後，我們透過X射線繞射儀、聚焦離子束系統和電子顯微鏡系統，對晶相和微結構進行驗證。接著，我們對以不同配方製作出之五種優選晶面的熱穩定性和硬度進行了比較研究。
2.透過電化學和應力分析，研究直流電鍍生成雙晶的機制。
我們使用旋轉環盤電極來分析不同添加劑組合對銅沉積行為的影響。不同添加劑比例導致亞銅離子和銅離子產生不同的反應中間體，進而對表面產生不同的應力，形成不同的晶面。因此，我們透過螺旋電鍍儀分析其中的應力變化，並結合這兩種分析方法，找出直流電鍍下生成雙晶的機制。

Copper electroplating is widely used in manufacturing commercial copper foils, copper clad laminate, and in the semiconductor industry. By adjusting electroplating parameters, we can fabricate different copper materials to specific needs. Recent studies have shown that copper with nanotwinned structures significantly improves mechanical properties, oxidation resistance, and catalytic performance, also addressing electron migration issues. While pulse electroplating is the conventional method for twin crystal production, it's rather time-consuming. This study aims to use direct current electroplating to produce copper foils in faster way with preferred crystal orientations by varying electroplating solution parameters. The study also aims to understand the mechanisms behind twinned structures formation through direct current electroplating, which lacks a comprehensive explanation compared to pulse electroplating. The research in this thesis has two primary directions:
1.Producing copper foils with preferred crystal orientations by adjusting the ratios of electroplating additives and current density.
Initially, we successfully fabricated copper foils with (111) nanotwinned structure, (200), (220) nanotwinned strcuture, and (220) preferred crystal orientations using different gelatin and chloride ion proportions. We verified crystal phases and microstructures using X-ray diffraction, focused ion beam systems, and electron microscopy. Subsequently, we compared the thermal stability and hardness of these four preferred crystal orientations.
2.Investigating the mechanism for twin crystal formation in direct current electroplating through electrochemical and stress analysis.
We employed a rotating ring-disk electrode to study the impact of various additive combinations on copper deposition behavior. Different additive ratios led to distinct reaction intermediates between cuprous ions and cupric ions, resulting in varying surface stresses and different crystal orientations. Our goal is to analyze stress variations using the spiral contractometer and combine both analysis methods to understand the mechanism for twin crystal formation in direct current electroplating.

摘要 iii
Abstract iv
致謝 vi
目錄 viii
圖目錄 xii
表目錄 xviii
1 第一章 緒論 1
1.1 前言 1
1.2 研究動機 1
2 第二章 文獻回顧 3
2.1 電化學原理與技術 3
2.1.1 電化學系統 3
2.1.2 電化學熱力學與動力學 5
2.1.3 電化學分析技術 8
2.1.4 流動系統之電化學分析 9
2.2 電鍍銅 11
2.2.1 電鍍銅系統 11
2.2.2 電鍍添加劑 16
2.2.3 陽極材料 27
2.2.4 奈米雙晶銅 29
2.2.5 明膠於電鍍銅上的應用 35
3 第三章 實驗流程與儀器簡介 39
3.1 實驗架構 39
3.2 化學藥品 39
3.2.1 電鍍銅 39
3.2.2 電化學拋光 40
3.3 儀器設備清單與原理 41
3.3.1 儀器設備清單 41
3.3.2 儀器設備原理 43
3.4 實驗步驟 50
3.4.1 前置作業 50
3.4.2 電鍍銅沉積之實驗流程 52
3.4.3 銅箔材料鑑定分析之樣品製備流程 53
3.4.4 銅箔材料應用分析之樣品製備流程 54
3.4.5 電化學分析之實驗流程 54
3.4.6 光譜分析之實驗架設 55
3.4.7 電鍍應力分析之實驗流程 56
4 第四章 結果與討論 58
4.1 不同電鍍參數與銅箔晶面之關係 58
4.1.1 明膠與氯離子組合所誘導之(111)雙晶銅晶面 59
4.1.2 明膠所誘導之(200)銅晶面 68
4.2 不同晶面之銅箔性質比較 71
4.2.1 熱穩定性比較 72
4.2.2 硬度的比較 75
4.3 利用電化學方法探討雙晶生長機制 77
4.3.1 不同添加劑組合所對應之銅還原機制 78
4.3.2 以RRDE於定電壓電鍍分析雙晶生長機制 84
4.4 利用螺旋應力儀探討雙晶生長機制 87
4.5 利用光譜分析探討添加劑於電鍍時的變化 90
5 第五章 結論與未來展望 92
5.1 結論 92
5.1.1 以電鍍添加劑製備具有雙晶結構之銅箔與其他優選晶面之銅箔 92
5.1.2 以電化學方法與應力量測分析雙晶生成之機制 92
5.2 未來展望 93
5.2.1 更完善的銅箔性質分析與半導體相關之應用 93
5.2.2 不同電鍍參數之應力分析系統建立 94
5.2.3 電化學分析與光譜分析及理論計算之結合 95
參考文獻 96

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