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研究生:林若蘋
研究生(外文):Jo-Ping Lin
論文名稱:鍍液劣化機制與其對矽導通孔中銅電沉積的影響
論文名稱(外文):Degradation of Electroplating Bath and its Influence on Copper Electrodeposition for Through-Silicon Via Filling
指導教授:蔡子萱蔡子萱引用關係
口試委員:黃瑞雄周偉龍吳永富
口試日期:2012-07-12
學位類別:碩士
校院名稱:國立臺北科技大學
系所名稱:資源工程研究所
學門:工程學門
學類:材料工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:92
中文關鍵詞:鍍液劣化矽導通孔添加劑
外文關鍵詞:Plating bathCopperDegradationTSVSPSPEG
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矽導通孔(TSV)電鍍銅製程為3D IC的重點技術,雖然已證實在鍍液中加入Polyethylene glycol(PEG)及聚二硫二丙烷磺酸鈉(SPS)有助於填孔,但是鍍液卻會因為與陽極金屬或鍍液存放系統接觸而劣化,以致隨時間增加,導孔內出現空洞或縫隙。本研究藉由電化學線性掃描伏安法、交流阻抗法、陽極剝除法以及高效液相層析儀監控添加劑於鍍液中的濃度,並探討時間、陽極材料、陽極面積大小及鍍液存放系統的影響。實驗結果發現與鉑接觸,不會使鍍液劣化,而與銅接觸,則容易使鍍液劣化;若將增加銅與鍍液的接觸面積,則會加速鍍液劣化。此外,本研究設計之隔膜系統有助於防止陰極區的添加劑直接與陽極區的銅粒接觸,有助於減緩鍍液劣化,並且能有效的阻隔添加劑從陰極區擴散到陽極。實驗更發現以CVS進行鍍銅液分析時,輔助電極銅的面積大會加速鍍液劣化,進而影響分析結果。最後,以HPLC監控PEG濃度發現,存放系統的材質對PEG濃度影響很大,不亞於與銅接觸的濃度遞減情形。本論文發現多項影響鍍液中添加劑濃度與作用的因素,並成功設計一減緩鍍液劣化的系統,相關參數與討論有助於改善TSV電鍍製程。

Copper eletrodeposition in through silicon via (TSV) is the key technology for three-dimensional integrated circuits. It has been confirmed that Polyethylene glycol(PEG) and Bis-(3-sodiumsulfopropyl disulfide) (SPS) as additives are helpful to fill the via for copper eletrodeposition. However, plating bath would degrade because it contacts anodic metal or is stored in an inappropriate vessel. The experiment used linear sweep voltammetry, impedance, cyclic voltammetry stripping (CVS) and High Performance Liquid Chromatography(HPLC) to monitor the concentration of additives in plating bath and to study the effects of time, anodic metal, surface area and storage vessels. The experimental result shows that plating bath would not degrade by contacting platinum, but would degrade by contacting copper. In addition, large surface area of copper makes the plating bath to degrade fast. In this study, a diaphragm system was designed to prevent the additives contacting the anode copper, decrease the degradation rate of plating bath. Still more, the experimental result shows that CVS analyzed the plating bath and increased the area of counter electrode make the plating bath to degrade fast. Finally, monitoring the concentration of PEG by HPLC shows that the material of plating bath storage vessels would drastically effect the concentration of PEG. The degree of PEG degradation due to the storage vessel is more serious than that due to contacting copper. The research designs a system to successfully decrease the degradation rate of plating bath. Relevant parameters and discussion are helpful to improve copper eletrodeposition in TSV.

目 錄

中文摘要 i
英文摘要 ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
1-1 三維積體電路簡介 1
1-2 TSV技術簡介 2
1-2-1 TSV電鍍系統 4
1-2-2 TSV銅電鍍的問題 6
1-3 研究動機 10
第二章 文獻回顧 11
2-1 旋轉電極分析TSV電鍍 11
2-2 PEG作用與劣化分析 13
2-3 SPS作用與劣化分析 14
2-4 其他劣化分析 14
第三章 基本原理 16
3-1 電化學分析原理 16
3-1-1 線性掃描伏安法 16
3-1-2 陽極剝除法 17
3-1-3 交流阻抗 18
3-2 旋轉圓盤電極邊界層理論 21
3-3 高效液相層析儀原理 22
3-4 離子交換膜作用原理 23
3-5 吸附的原理 24
第四章 實驗流程 26
4-1 實驗藥品與耗材 26
4-2 實驗設備 26
4-3 實驗方法 27
4-3-1 鍍液劣化研究系統 27
4-3-2 鍍銅液的電化學分析 27
4-3-3 添加劑的耗損分析 31
第五章 結果與討論 33
5-1 陽極材料對鍍液劣化的影響 33
5-1-1 PEG濃度 33
5-1-2 SPS濃度 42
5-2 銅陽極表面積對鍍液劣化的影響 52
5-2-1 PEG濃度 52
5-2-2 SPS濃度 58
5-3 隔膜系統對鍍液劣化的影響 65
5-3-1 PEG濃度 65
5-3-2 SPS濃度 74
5-4 存放系統對鍍液劣化的影響 84
5-5 輔助電極對ASV分析的影響 85
第六章 結論 88
參考文獻 89



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