臺灣博碩士論文加值系統

本研究目標為開發一可在短時間內完成超級填充(Super-filling)之填孔配方。電鍍系統中選用在高電流密度操作下具有長時間穩定性的尺寸安定性陽極及具有較長使用壽命的加速劑DPS。而本研究在此電鍍系統中，針對添加劑間的交互作用及物理參數如對流強度、操作溫度等的影響進行分析討論。
由結果發現，氯離子的吸附覆蓋率能主導複合抑制劑PEG-Cl- 的抑制效果，並且是影響在高電流密度下可否形成孔底上移(Bottom-up)的關鍵。而氯離子的吸附覆蓋率與對流強度呈正相關，因此填孔表現也與對流強度呈現正相關性。在強對流系統中，填孔表現與溫度成正比；在弱對流系統中，填孔表現則受到銅離子的質傳控制。另外，欲完成無空洞的通孔填充，其關鍵在於銅離子在孔中的質傳能力，因此可藉由強制對流在孔中形成對稱性的流場，加上低溫操作與高分子量聚乙二醇(PEG)的使用，達到通孔的快速填充。

To develop copper plating formulation for high-speed vias filling, a more stable insoluble anode, namely dimensionally stable anode (DSA), was used at high current density. We choose a novel accelerator, 3-(N,N-Dimethylthiocarbamoyl)-thio propanesulfonic acid (DPS), which has a longer lifetime in the DSA system and better performance for acceleration on copper superfilling deposition. This research investigates the influence of filling behavior between experimental condition and interaction of additives.
According to the results, the inhibition ability of complex inhibitor (PEG-Cl-) was positively in correlation with convection and filling performance of blind via filling. In a plating system with a strong forced convection and a low temperature exhibited better filling performance. Comparatively, the filling performance was Cu(II) mass-transfer controlled in the weakly forced convection system. And the most significant effect of void-free filling was the transport of cupric ion to the center of through hole in a symmetrical flow field.

摘要-i
Abstract-ii
目錄-iii
圖目錄-v
表目錄-viii
第1章 緒論
第1-1節 前言-p.1
第1-2節 研究動機與目的-p.2
第2章 文獻回顧與理論
第2-1節 電化學理論-p.3
2-1.1 電化學極化與過電位 -p.3
2-1.2 電子轉移與質傳控制-p.5
第2-2節 電鍍基本原理-p.9
第2-3節 金屬化製程-p.10
2-3.1 銅製程技術-p.10
2-3.2 填孔電鍍製程-p.13
第2-4節 酸性電鍍銅-p.23
2-4.1 電鍍添加劑-p.23
2-4.2 電鍍銅陽極材料-p.46
2-4.3 電鍍方式-p.48
第2-5節 電化學分析方法-p.50
2-5.1 線性掃描伏安法 (Linear Sweep Voltammetry, LSV)-p.50
2-5.2 循環伏安法 (Cyclic Voltammetry, CV)-p.51
2-5.3 計時電位/電流分析法-p.52
第3章 實驗藥品、裝置與步驟
第3-1節 實驗藥品-p.53
第3-2節 實驗陽極材料-p.54
第3-3節 實驗裝置-p.55
3-3.1 電鍍實驗裝置-p.55
3-3.2 恆電位/電流儀 (Potentiostats / Galvanostats)-p.58
3-3.3 金相顯微鏡 (Optical Microscope, OM)-p.59
第3-4節 實驗步驟-p.60
3-4.1 哈林試驗槽電鍍實驗 -p.60
3-4.2 電化學分析實驗-p.61
第4章 實驗結果與討論
第4-1節 尺寸安定性陽極系統 -p.62
4-1.1 尺寸安定性陽極材料之選擇-p.62
4-1.2 電鍍添加劑之選擇-p.62
4-1.3 陽極反應對電鍍填充之影響-p.67
第4-2節 高速盲孔填充之配方研究-p.70
4-2.1 新穎平整劑於盲孔填充之開發-p.70
4-2.2 氯離子對盲孔填充之影響-p.79
4-2.3 對流效應對盲孔填充之影響-p.85
4-2.4 溫度對盲孔填充之影響-p.88
第4-3節 高速通孔填充之配方研究-p.102
4-3.1 強制對流對通孔填充之影響-p.102
4-3.2 氫離子濃度對通孔填充之影響-p.105
4-3.3 氯離子濃度對通孔填充之影響-p.107
4-3.4 溫度對通孔填充之影響-p.109
第5章 結論
5-1.1 加速劑DPS於尺寸安定性陽極系統的作用分析-p.112
5-1.2 高速盲孔填充之配方研究-p.112
5-1.3 高速通孔填充之配方研究-p.113
第6章 未來研究方向
6-1.1 加速劑DPS於尺寸安定性陽極系統的作用分析-p.114
6-1.2 高速導孔填充之配方研究-p.114
第7章 參考文獻

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