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研究生:黃國瑋
研究生(外文):Huang,Kuowei
論文名稱:電子應用中微深孔銅沉積填滿程序的一種簡易新型監測方法
論文名稱(外文):A novel monitoring method for the micro-via filling process by copper electrodeposition in the application of electronics
指導教授:楊文彬楊文彬引用關係
指導教授(外文):Yang, Wenbin
口試委員:鄭文桐朱錦明
口試委員(外文):Jeng,WentungJu,Jinming
口試日期:民國一百年七月二十六日
學位類別:碩士
校院名稱:國立聯合大學
系所名稱:化學工程學系碩士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:中文
論文頁數:91
中文關鍵詞:電鍍添加劑對流吸附協合效應微盲孔
外文關鍵詞:electroplatingadditivesconvection-dependent adsorptionsynergymicro-via
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實驗以低銅高酸鍍液為基礎,使用電化學分析儀做循環線性掃描伏安法(CLSV)和定電位分析,觀察添加劑的吸附行為、協合效應、競爭效應、穩定性,以及模擬真實電鍍時因長時間電鍍而添加劑消耗的情況,藉以監測鍍液中添加劑濃度是否為一定。再進行晶片電鍍以及使用掃描式電子顯微鏡,觀察表面鍍層和孔洞鍍層之填滿型態。
由實驗結果顯示,第一,添加劑2-MP在高電壓(-0.65V)較無吸附能力,且其電流值與轉速平方根成一線性,此應與電極上阻力膜的薄與厚有關,而在定電壓下,若不同順序加入添加劑,發現優先加入抑制劑或是平整劑時,最後的電流值皆較小,此意謂吸附性的順序與抑制的電流量有關;第二,在低電壓不同轉速時,可發現2-MP在高轉速時抑制的電流比低轉速來的大,顯示2-MP有選擇性的對流吸附(CDA);第三,利用前述作用,若液中無2-MP時,鍍液則不會有對流吸附的效果,因此與母液的電流差為負值,藉此可判斷鍍液中添加劑濃度是否維持一定;及第四,模擬加速劑在孔底累積的結果,隨著MPSA 、Cl-濃度等比例增加時,轉速1000 rpm(孔外)的電流皆大於100 rpm(孔內),預測不利於導通孔的電鍍,但與晶片電鍍結果不符合,故判斷加速劑於孔底因少許累積效果,使電鍍型態較好。

In this study, we use low-copper and high-acid copper sulfate solution as basic bath, to characterize the physical and chemical interactions between these additives and copper ions by cyclic linear sweep voltammetric(CLSV) and potentiostatic measurements. In order to monitor the concentration of additives, we simulate the consumption of additves in the electroplating. Finally, the characteric of the deposited copper on chips were studied by scanning electron microscopy, for observing the construction of via hole.
The result showed that adsorption of additives got worse at higher voltage, and the current was proportional to square root of angular speed (rpm). Four of potentiostatic measurements, first, the different order of additives, if leveler and suppressor added to bath at first, the current was the lowest. The current of 2-MP (leveler) at low-rpm was better than that at high-rpm at lower voltage because of convection-dependent adsorption (CDA). In addition, according to CDA function, we could monitor the concentration of 2-MP was enough. The concentration of accelerator accumulates in via hole, the higher concentration of MPSA and Cl-, the current of 1000 rpm(surface) higher than 100 rpm (bottom of via hole), so we predicted that deposition of via hole was worse, and we could deposit on chip to confirm it.

誌謝
中文摘要
英文摘要
第一章 序論
第二章 文獻回顧
2-1電子構裝的發展
2-2 金屬化製程及導線之材料
2-2-1金屬化製程
2-2-2 金屬薄膜的沉積之比較
2-2-3銅製程之興起
2-2-4銅擴散阻障層與晶種層
2-3銅電鍍的原理
2-3-1銅沉積的反應機制
2-3-2極化作用的種類
2-4電鍍液的組成
2-4-1氫離子(H+)
2-4-2氯離子(Cl-)
2-4-3抑制劑(Suppressor)
2-4-4光澤劑(Brighteners & Accelerator)
2-4-5平整劑(Leveler)
2-5鍍液中添加劑的檢測方法
2-5-1 CVS (Cyclic Voltammertric Stripping)
2-5-2 LC (Liquid Chromatography)
第三章 實驗
3-1實驗藥品與儀器
3-1-1實驗藥品
3-1-2實驗儀器
3-2實驗步驟
3-2-1電化學分析實驗
3-2-2 電化學電鍍銅實驗
3-3 理論厚度計算
3-4相對沈積厚度
第四章結果與討論
4-1循環伏安分析法(CLSV)
4-1-1母液之分析
4-1-2 PEG(10000) 抑制劑之分析
4-1-3 平整劑(2-MP)之分析
4-1-4 平整劑(OP)之分析
4-1-5 MPSA光澤劑之分析
4-1-6 添加劑間之競爭與協合作用
4-1-7鍍液中工作電極轉速與溫度對添加劑的影響
4-2定電壓下鍍液中添加劑間協合與競爭效應
4-3 晶片微電鍍鍍層形態分析
4-3-1 晶片表面形態分析
4-3-2 晶片孔洞鍍層剖面形態分析
4-4簡易監測添加劑對孔洞填滿之相對分析
第五章 結論
參考文獻

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