臺灣博碩士論文加值系統

本研究為利用超臨界二氧化碳(SC-CO2)電鍍來探討平面銅電鍍特性變化，並以陽極氧化鋁膜板為基板製備銅奈米線。超臨界二氧化碳銅電鍍操作壓力為10.2～20.4MPa、溫度35℃、攪拌轉速350rpm，結果發現在超臨界二氧化碳下電鍍，銅膜為多結晶之結構；且晶粒尺寸隨著壓力的增加而減小，根據文獻壓力可以加快成核速率與超臨界下形成的乳化鍍液具有週期電鍍特性(periodic-plating-characteristic)，這類似脈衝電鍍效果，導致晶粒尺寸減小，壓力0.1MPa時晶粒尺寸58.6nm，隨著壓力上升至13.6MPa時晶粒尺寸減小至52.1nm。且銅膜硬度隨著晶粒尺寸的減小而上升，由常壓下0.1MPa晶粒尺寸58.6nm時的0.48GPa，提升至超臨界二氧化碳下13.6MPa晶粒尺寸52.1nm時的2.51GPa，機械性質整整提高約5倍。此外，在超臨界二氧化碳下進行奈米孔洞電鍍反應，比常壓電鍍具有較高的填孔率，因為在超臨界二氧化碳下幾乎沒有表面張力。

This study is to investigate the characteristic of copper electroplating in supercritical carbon dioxide(SC-CO2) electroplating process, and to apply this technology to produce Cu-nanowires in anodic aluminum oxide template. SC-CO2 is electroplating with operation pressure form 10.2 to 20.4MPa and temperature at 35℃, fixed rotational speed 350 rpm. Experimental result reveals, that the Cu-film is polycrystalline structure, and that the grain size of the Cu-film decreases with increasing pressure under SC-CO2 electroplating. According to the reference：(i) pressure can enhance nucleation rate, (ii) the emulsified electrolyte by SC-CO2 have a periodic plating characteristic when Sc–CO2–E is applied； this acts like pulsation electroplating leading to a decrease in grain size. At 0.1MPa the grain size is 58.6nm. By increasing the pressure to 13.6MPa, the grain size is reduced to 52.1nm. It was found that the copper film hardness is highly dependent on the grain size. For example, Cu-film at generated 0.1MPa hardness of the resulting Cu-film is 0.48GPa；in contrast, the hardness is about five-time higher 2.51GPa when the Cu-film was generated at 13.6MPa. In addition, the electroplating in supercritical carbon dioxide have higher filling rate rather than in ambient condition, because SC-CO2 has extremely low surface tension.

目錄
中文摘要．．．．．．．．．．．．．．．．．．．．．．．．I
Abstract．．．．．．．．．．．．．．．．．．．．．．．．II
目錄．．．．．．．．．．．．．．．．．．．．．．．．．．IV
圖目錄．．．．．．．．．．．．．．．．．．．．．．．．．VIII
表目錄．．．．．．．．．．．．．．．．．．．．．．．．．XIII
第一章 緒論．．．．．．．．．．．．．．．．．．．．．．1
第二章 文獻回顧．．．．．．．．．．．．．．．．．．．．4
2.1 電鍍．．．．．．．．．．．．．．．．．．．．．．．4
2.1.1 電鍍的原理．．．．．．．．．．．．．．．．．4
2.1.2 銅電鍍．．．．．．．．．．．．．．．．．．．6
2.1.3 銅電鍍之添加劑．．．．．．．．．．．．．．．10
2.2 超臨界電鍍．．．．．．．．．．．．．．．．．．．16
2.2.1超臨界流體．．．．．．．．．．．．．．．．16
2.2.2 超臨界二氧化碳．．．．．．．．．．．．．．18
2.2.3 超臨界二氧化碳乳化鍍液-界面活性劑．．．．．22
2.2.4 超臨界二氧化碳乳化電鍍．．．．．．．．．．．27
2.2.5 超臨界電鍍影響參數．．．．．．．．．．．．．31
2.2.6 超臨界二氧化碳銅電鍍．．．．．．．．．．．．37
2.3 陽極氧化鋁．．．．．．．．．．．．．．．．．．．42
2.3.1陽極氧化鋁介紹．．．．．．．．．．．．．．42
2.3.2 生長機制．．．．．．．．．．．．．．．．．．44
2.3.3 阻擋層(barrier layer) ．．．．．．．．．．．．．46
2.4 究動機與目的．．．．．．．．．．．．．．．．．．49
第三章 實驗方法與步驟．．．．．．．．．．．．．．．50
3.1 藥品與儀器．．．．．．．．．．．．．．．．．．．50
3.1.1 藥品．．．．．．．．．．．．．．．．．．．50
3.1.2 實驗儀器．．．．．．．．．．．．．．．．．51
3.1.3 高壓反應設備．．．．．．．．．．．．．．．52
3.1.4 分析儀器．．．．．．．．．．．．．．．．．53
3.2 實驗架構與流程圖．．．．．．．．．．．．．．．．54
3.2.1 實驗流程圖．．．．．．．．．．．．．．．．55
3.3 超臨界電鍍實驗架設及其電流效率計算．．．．．．．56
3.3.1 超臨界電鍍實驗架設．．．．．．．．．．．．56
3.3.2 電流效率計算．．．．．．．．．．．．．．．．60
3.4 陽極氧化鋁模板．．．．．．．．．．．．．．．．．62
3.4.1 基材前處理．．．．．．．．．．．．．．．．62
3.4.2 陽極氧化鋁製備．．．．．．．．．．．．．．63
3.4.3 填孔率分析之試片處理．．．．．．．．．．．．67
3.5 銅電鍍．．．．．．．．．．．．．．．．．．．．．68
3.5.1改變操作壓力銅上銅電鍍．．．．．．．．．．69
3.5.2陽極氧化鋁上銅電鍍．．．．．．．．．．．．71
3.6 分析儀器介紹．．．．．．．．．．．．．．．．．．72
3.6.1掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) ．．．．．．．．．．．．．．．．．．．72
3.6.2 X-Ray繞射儀(X-Ray Diffraction, XRD) ．．．．．73
3.6.3 能量散射光譜儀(Energy Dispersive Spectrometers, EDS) ．．．．．．．．．．．．．．．．．．．74
3.6.4 奈米壓痕試驗機(Triboscope, Hysitron USA) ．．．75
3.6.5 原子力顯微鏡(Atomic Force Microscope, AFM) ．77
第四章 結果與討論．．．．．．．．．．．．．．．．．．78
4.1 電流效率與乳化的討論．．．．．．．．．．．．．．79
4.2 電鍍銅膜探討．．．．．．．．．．．．．．．．．．84
4.2.1 表面形貌分析．．．．．．．．．．．．．．．84
4.2.2 結晶構造分析．．．．．．．．．．．．．．．97
4.2.3 機械性質分析．．．．．．．．．．．．．．．100
4.3 銅奈米線探討．．．．．．．．．．．．．．．．．．102
4.3.1 陽極氧化鋁形態觀察．．．．．．．．．．．．．102
4.3.2 結晶構造分析．．．．．．．．．．．．．．．．103
4.3.3 填孔率比較．．．．．．．．．．．．．．．．105
4.3.4 阻擋層效應．．．．．．．．．．．．．．．．．111
第五章 結論與未來展望．．．．．．．．．．．．．．．119
5.1 結論．．．．．．．．．．．．．．．．．．．．．．119
5.2 未來展望．．．．．．．．．．．．．．．．．．．．121
參考文獻．．．．．．．．．．．．．．．．．．．．．．．．122

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