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研究生： 林德瑋
Lin, De-Wei
論文名稱： 利用超臨界二氧化碳電鍍法於經熱處理之陽極氧化鋁模板進行奈米孔銅金屬沉積之研究
Application of supercritical carbon dioxide electrodeposition for copper filling into nano-holes in heat-treated anodic aluminum oxide template
指導教授： 蔡文達
Tsai, Wen-Ta
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2017
畢業學年度： 105
語文別： 中文
論文頁數： 96
中文關鍵詞： 奈米孔洞 、銅金屬電沉積 、陽極氧化鋁陣列 、超臨界二氧化碳電鍍
外文關鍵詞： metal filling, high aspect ratio nano-hole, anodic aluminum oxide template, supercritical carbon dioxide electrodeposition
相關次數： 點閱：156  下載：10 
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    • 本研究以熱處理的方法將陽極氧化鋁模板進行改質以降低其親水後，利用乳化超臨界二化碳電鍍法進行高深寬比奈米孔洞之金屬填充。經過陽極氧化後之鋁模板在860 oC/24h熱處理後，其厚度約為5 m，孔洞直徑約為60 nm，深寬比為83左右。銅金屬電鍍填孔是在50 oC、10 MPa的壓力下於含有約40%的乳化超臨界二氧化碳流體及60%硫酸銅水溶液之電解液中進行。電沈積之後，利用掃描式電子顯微鏡(SEM)、穿透式電子顯微鏡(TEM)及能譜散射分析儀(EDS)對試片進行分析。實驗結果顯示：乳化超臨界二氧化碳電鍍法可以在疏水性的高深寬比奈米孔洞中有效進行金屬銅電鍍沉積，優於常壓下之傳統電鍍。

    Copper metal filling into heat-treated anodized aluminum oxide (AAO) nano-array holes was attempted by electrodeposition involving emulsified supercritical carbon dioxide (sc-CO2) fluid, in comparison with that performed using conventional process at ambient pressure. The AAO template was likely hydrophobic in nature after being heat treated at 860 oC/24h. It had a dimension of about 5 um in thickness with an average hole-size of 60 nm and an aspect ratio of 83. Copper electrodeposition was conducted at 50 oC and at a pressure of 10 Mpa in an electrolyte consisting of 40 vol% of sc-CO2 and 60 vol% of CuSO4 aqueous solution. Both constant potential (-0.4 VPt, -0.5 VPt, -0.6 VPt) and constant current density (-10 mA/cm2) conditions were applied for metal filling. After electrodeposition, the extent of metal filling was examined using a scanning electron microscope (SEM) , and a transmission electron microscope (TEM), both coupled with an energy dispersive spectrometer (EDS). When as-anodized AAO template was used, a higher filling efficiency (in terms of cross section area percentage) was found in sc-CO2 bath than in conventional bath. When heat-treated AAO template was used, copper filling into the high aspect ratio nano-holes could be successfully achieved by sc-CO2 electrodeposition, while it was not possible in conventional bath. The advantage of sc-CO2 electrodeposition over that of conventional process was mainly attributed to the change of hydrophobicity of AAO template induced by heat treatment.

    總目錄 摘要……………………………………………………………………………I Extended Abstract……………………………………………………….……II 致謝…………………………………………………………………….XIII 總目錄…………………………………………………………………...…XV 表目錄……………………………………………………………...……XVIII 圖目錄……………………………………………………………………XIX 第一章 前言…………………………………………………………………1 第二章 文獻回顧……………………………………………………………4 2-1陽極氧化鋁(Anodic Aluminum Oxide, AAO)…………………4 2-1-1 陽極氧化鋁生長機制……………………………………4 2-1-2 製備陽極氧化鋁模板……………………………………5 2-1-3 陽極氧化鋁表面性質與改質……………………………8 2-2 超臨界流體概論………………………………………………10 2-2-1 超臨界二氧化碳流體之性質及應用…………………11 2-2-2 微乳化機制……………………………………………12 2-2-3 界面活性劑所扮演的角色……………………………12 2-3 高深寬比電鍍填孔…………………………………………14 2-3-1 一般常壓電鍍填孔……………………………………15 2-3-2 超臨界二氧化碳電鍍填孔……………………………16 2-4 定電位電鍍與定電流密度電鍍之差異……………………..17 第三章 實驗步驟…………………………………………………………39 3-1 多孔陽極氧化鋁模板製備…………………………………39 3-1-1試片前處理……………………………………………39 3-1-2電解拋光………………………………………………39 3-1-3 兩階段陽極處理………………………………………39 3-1-4 披覆保護層……………………………………………40 3-1-5 移除鋁基材……………………………………………40 3-1-6 移除阻絕層……………………………………………41 3-1-7 移除保護層……………………………………………41 3-2 陽極氧化鋁片熱處理…………………………………………41 3-3 披覆導電層及電鍍陰極製備…………………………………42 3-4 填孔處理………………………………………………………42 3-4-1 超臨界槽體電鍍設備…………………………………43 3-4-2 CV測試………………………………………………43 3-4-3 填孔處理………………………………………………44 3-5樣品分析………………………………………………………44 3-5-1 陽極氧化鋁結構組織鑑定……………………………44 3-5-2 填孔鑑定………………………………………………45 3-5-3 潤濕性分析……………………………………………45 3-6 移除陽極氧化鋁模板以獲得奈米線…………………………45 第四章 結果與討論………………………………………………………53 4-1 陽極氧化鋁模板分析………………………………………53 4-1-1 陽極氧化鋁模板………………………………………53 4-1-2 陽極氧化鋁模板接觸角量測…………………………54 4-2 填孔分析……………………………………………………54 4-2-1循環伏安法測試…………………………………………54 4-2-2 電位對還原電流影響…………………………………55 4-2-3 定電位填孔結果分析…………………………………56 4-2-4 電位、電流對填孔結果的影響………………………59 4-2-5定電流密度填孔分析……………………………………60 4-3 綜合討論………………………………………………………62 4-4 移除氧化鋁基板及銅奈米線結構觀察………………………64 第五章 結論………………………………………………………………90 第六章 未來研究方向……………………………………………………91 參考文獻…………………………………………………………………….92

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