Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3823
標題: 通孔填充電鍍銅之配方開發
Development of New Formula for Filling Through-Hole by Copper Electroplating
作者: 盧俊瑋
Lu, Chun-Wei
關鍵字: Copper Electroplating;電鍍銅;Through-hole Filling;Butterfly technology;Electroplating Additives;轉速效應;通孔電鍍;蝴蝶技術;電鍍添加劑
出版社: 化學工程學系所
引用: 1. H. Xiao, Introduction of Semiconductor Manufacturing Technology, Prentice-Hall Inc., New Jersey, 2001. 2. P. C. Andricacos, C. Uzoh, J. O. Dukovic, J. Horkans, and H. Deligianni, “Damascene Copper Electroplating for Chip Interconnections,” IBM J. Res. & Dev., 42, 567-574, 1998. 3. 竇維平,黃河樹,蘇勇誌,與顏銘瑤,「電鍍銅添加劑在 IC 及 IC 構裝基板上的應用」,化工,第50卷第4期,14-29,2003。 4. M. R. Kalantary, D. R. Gabe, and M. R. Goodenough, “Unipolar and Bipolar Pulsed Current Electrodeposition for PCB Production,” J. Appl. Electrochem., 23, 231-240, 1993. 5. 胡啟章,電化學原理與方法,五南出版,2002。 6. A. J. Bard, and L. R. Faulkner, Electrochemical Methods Fundamentals and Applications, John-Woely & Sons Inc., New York, USA, 2001. 7. M. Georgiadou, D. Veyret, R. L. Sani, and R. C. Alkire, “Simulation of Shape Evolution during Electrodeposition of Copper in the Presence of Additive”, J. Electrochem. Soc., 148, C54-C58, 2001. 8. Z. Nagy, J. P. Blaudeau, N. C. Hung, L. A. Curtiss, and D. J. Zurawski, “Chloride Ion Catalysis of the Copper Deposition Reaction”, J. Electrochem. Soc., 142, L87-L89, 1995. 9. D. M. Soares, S. Wasle, K. G. Weil, and K. Doblhofer, “Copper Ion Reduction Catalyzed by Chloride Ions,” J. Electroanal. Chem., 532, 353-358, 2002. 10. G. M. Brown, and G. A. Hope, “A SERS Study of SO42- / Cl- ion adsorption at a Copper Electrode In-Situ,” J. Electroanal. Chem., 405, 211-216, 1996. 11. W. P. Dow, and C. W. Liu, “Evaluating the Filling Performance of a Copper Plating Formula Using a Simple Galvanostat Method,” J. Electrochem. Soc., 153, C190-C194, 2006. 12. W. P. Dow, M. Y. Yen, C. W. Liu, and C. C. Huang, “Enhancement of filling performance of a copper plating formula at low chloride concentration,” Electrochimica Acta, 53, 3610-3619, 2008. 13. M. Yokoi, S. Konishi, and T. Hayaashi, “Adsorption Behavior of Polyoxyenthylene Glycol on the Copper Surface in an Acid Copper Sulphate Bath”, Denki Kagaku., 52, 218, 1984. 14. J. J. Kelly and A. C. West, “Copper Deposition in the Presence of Polyethylene Glycol I Quartz Crystal Microbalance Study”, J. Electrochem. Soc., 145, 3472-3476, 1998. 15. Z. V. Feng, X. Li, and A. A. Gewirth, “Inhibition Due to the Interaction of Polyethylene Glycol, Chloride, and Copper in Plating Baths: A Surface-Enhanced Raman Study”, J. Phys. Chem. B, 107, 9415-9423, 2003. 16. B. G. Xie, J. J. Sun, X. B. Chen, J. H. Chen, T. L. Xiang, and G. N. Chen, “In Situ Monitoring of Additives in Copper Plating Baths by Cyclic Voltammetric Stripping with a Microelectrode”, J. Electrochem. Soc., 154, D516-D519, 2007. 17. W. P. Dow, M. Y. Yen, W. B., Lin, and S. W. Ho, “Influence of Molecular Weight of Polyethylene Glycol on Microvia by Copper Electroplating”, J. Electrochem. Soc., 152, C769-C775, 2005. 18. C. C. Hung, Y. L. Wang, W. H. Lee, and S. C. Chang, “Competitive Adsorption Between Bis(3-sodiumsulfopropyl disulfide) and Polyalkylene Glycols on Copper Electroplating”, J. Electrochem. Soc., 155, H669-H672, 2008. 19. J. Mendez, R. Akolkar, and U. Landau, “Polyether Suppressors Enabling Copper Metallization of High Aspect Ratio Interconnects”, J. Electrochem. Soc., 156, D474-D479, 2009. 20. N. Zukauskaite, and A. Malinauskas, “Electrocatalysis by a Brightener in Copper Electrode in Situ,” Sov. Electrochem., 24, 1564, 1989. 21. J. P. Healy, and D. Pletcher, “The Chemistry of the Additives in an Acid Copper Electroplating Bath PartII. The Instability of 4, 5- Dithiaoctane-1, 8-Disulphonic Acid in the Bath on Open Circuit,” J. Electroanaly. Chem., 338, 167, 1992. 22. E. Mattsson, and J. O. M. Bockris, “Galvanostatic Studies of the Kinetic of Deposition and Dissolution in the Copper + Copper Sulphate System,” Trans. Faraday Soc., 55, 1586, 1959. 23. W. P. Dow, H. S. Huang, M. Y. Yen, and H. H. Chen, “Roles of Chloride ion in Microvia Filling by Copper Electrodeposition - II. Studies Using EPR and Galvanostatic Measurements,” J. Electrochem. Soc., 152, C77-C88, 2005. 24. G. K. Gomma, “Effect of Azole Compounds on Corrosion of Copper in Acid Medium,” Materials Chemistry and Physics., 56, C27, 1998. 25. W. P. Dow, H. S. Huang, M. Y. Yen, and H. C. Huang, “Influence of Convection-Dependent Adsorption of Additives on Microvia Filling by Copper Electroplating,” J. Electrochem. Soc., 152, C425-C434, 2005. 26. K. Kondo, Y. Suzuki, T. Saito, “Shape Evolution of Electrodeposited Bumps with Shallow and Deep Cavities,” J. Electrochem. Soc., 156, D548-D552, 2009. 27. T. Oritani, N. Fukuhara, T. Okajima, F. Kitamura, and T. Ohsaka, “Electrochemical and Spectroscopic Studies on Electron-Transfer Reaction Between Novel Water-Soluble Tetrazolium Salts and a Superoxide Ion,” Inorganica Chimica Acta, 357, 436-442, 2004. 28. K. Umemoto, “Electrochemical Studies of the Reduction Mechanism of Tetrazolium Salts and Formazans,” Bull Chem. Soc. Jpn., 62, 3783-3789, 1989. 29. B. H. J. Bielski, G. G. Shiue, and S. Bajuk, “Reduction of Nitro Blue Tetrazolium by CO2- and O2- Radicals,” J. Phys. Chem., 84, 830-833, 1980. 30. K. Umemoto, Y. Nagase, and Y. Sasaki, “Reaction of Hydroxide Ion with Electron Donors in Aprotic solvents,” Bull Chem. Soc. Jpn., 67, 3245-3248, 1994. 31. K. Umemoto, and N. Okamura, “Reaction of Hydroxide Ion with Electron Acceptors in Dimethyl Sulfoxide,” Bull Chem. Soc. Jpn., 59, 3047-3052, 1986. 32. 汪建民,材料分析,中國材料科學學會,2001。 33. 羅吉宗,薄膜科技與應用,全華圖書,2005。 34. R. E. Lee, Scanning Electron Microscopy and X-Ray Microanalysis, Prentice-Hall: Englewood Cliffs, NJ, 1993. 35. 柯以侃,儀器分析,新文京開發出版,2005。 36. T. P. Moffat, J. E. Bonevich, W. H. Huber, A. Stanishevsky, and D. Josell, “Superconformal Electrodeposition of Copper in 500-90nm Features,” J. Electrochem. Soc., 147, 4524-4535, 2000. 37. J. J. Kelly, and A. C. West, “Leveling of 200nm Featires by Organic Additives,” Electrochem. Solid-State Lett., 2, 561-563, 1999. 38. K. Takeshi, K. Junichi, and M. Kuniaski, “Influence of Bath Composition to Via-Filling by Copper Electroplating,” J. J. Insitute of Electronics., 7/1, 2000. 39. 竇維平,「電鍍銅填充盲孔之技術發展」,電路板會刊第四十八期,第4-15頁,民國99年。 40. W. P. Dow, H. H. Chen, M. Y. Yen, W. H. Chen, and K. H. Hsu, “Through-Hole Filling by Copper Electroplating,” J. Electrochem. Soc., 155, D750-D757, 2008. 41. W. P. Dow, M. Y. Yen, S. Z. Liao, and Y. D. Chiu, “Filling Mechanism in Microvia Metallization by Copper Electroplating,” Electrochimica Acta, 53, 8228-8237, 2008. 42. S. C. Chang, J. M. Shieh, K. C. Lin, and B. T. Dai, “Wetting Effect on Gap Filling Submicron Damascene by an Electrolyte Free of Levelers,” J. Vac. Sci. Technol. B, 20, 1311-1316, 2002. 43. W. P. Dow, Y. D. Chiu, and Y. M. Yen, “Microvia Filling by Cu Electroplating Over a Au Seed Layer Modified by a Disulfide,” J. Electrochem. Soc., 156, D155-D167, 2009. 44. S. Soukane, S. Sen, and T. S. Caleb, “Feature Superfilling in Copper Electrochemical Deposition,” J. Electrochem. Soc., 149, C74-C81, 2002. 45. 陳祥豪,碩士論文,「填充微米級導孔與通孔之電鍍銅配方研究」,國立雲林科技大學,民國93年。 46. L. Xu, P. Dixit, J. Miao, and J. H. Pang, “Through-wafer Electroplated Copper Interconnect with Ultrafine Grains and High Density of Nanotwins,” Applied Physics Letters, 90, 033111, 2007. 47. N. Lin, J. Miao, and P. Dixit, “Mechanical and Microstructural Characterization of Through-Silicon Via Fabricated with Constant Current Pulse-Reverse Modulation,” J. Electrochem. Soc., 157, D323-D327, 2010. 48. P. Dixit, and J. Miao, “Aspect-Ratio-Dependent copper Electrodeposition Technique for Very High Aspect-Ratio Through-Hole Plating,” J. Elctrochem. Soc., 153, G552-G559, 2006. 49. 廖國良,碩士論文,「化學添加劑對於化學方法製備銅奈米顆粒及銅薄膜於聚亞醯胺上之特性研究」,國立中興大學,民國98年。
摘要: 
電子產品要求尺寸越來越小,其優點:降低封裝的面積、更輕量化、更密集的連結密度、更高的可靠度,和在低電阻中表現更優異的電子性能。傳統印刷電路板電鍍通孔時,均擲力需達到100%。近年來雖然有人研究通孔電鍍,但電鍍結果效果不彰,吾人開發出新穎電鍍添加劑,利用陰極旋轉方式加上蝴蝶填孔技術,提高電流密度至9ASF,可縮短電鍍時間為2小時,完成填孔電鍍製程。
一般而言,平整劑是含四級銨 (N+) 的有機雜環化合物 (Azole Compound),藉由電化學分析法證實於混合多種添加劑之間的協合效應,混合多種添加劑有助於提高電流密度的需求及加強抑制劑的濃度梯度;給予微弱且固定的強制對流情況下,有相輔相成的效果,同樣也營造出孔中先行銅沉積的行為。
在硫酸系統下,透過線性掃描伏安法和計時電位分析法,銅電極在不同轉速下的方法被利用來研究此添加劑的特徵。電化學分析結果可顯示添加劑在電極表面位置上的電化學吸附能力。根據電化學分析之結果發現,此添加劑抑制銅沉積之行為與其濃度成正比,濃度越高,其脫附電位愈負,表現出多層吸附或是電化學聚合的行為。
最後吾人利用開發的新穎配方直接填通孔電鍍。孔徑為50um,深度為380um,深寬比高達7.6,電鍍時間只需要9小時便可完全填充。

The size of electronic products is requested to be smaller and smaller. They provide several advantages such as reduced packaging area, light weight, higher interconnection density, high reliability, and excellent electrical performance with lower resistance. For traditional electroplating through hole, the throwing power of 100% have to achieve then it can meet the requirement. In recent years, many people studied the through hole electroplating. However, they need a conducting layer to be assembled at the bottom to improve the process. We consider to develop a new formula for filling through-hole by copper electroplating, and we use butterfly technology (BFT) to fill up the through hole. It can be processed at high current density, and reduce electroplating time to filling up.
In general, levelers bares tetrazolium compound, electrochemical analysis can characterize the additives' interaction in between. High current density could be applied and when multi-component formula was employed. In addition, multi-component formula can enhance the concentration gradient in the through hole. The filling performance of the multi-component formula could be enhanced with which weak and fixed forced convection combined. It could result in center-up filling mode.
In sulfuric acid system, linear sweep voltammetry (LSV) and chronopotentiometry (CP) were employed to characterize these additives on copper electrode at different rotating speeds. The electrochemical analyses reveal the adsorptive ability of these additives on copper electrode. According to the electrochemical analyses, the inhibiting effect of the additive on copper deposition depends on the its concentration, that is, the higher the additive concentration, the more negative the desorption potential. This suggests that the adsorption of the additive may be multilayer or it may perform electrochemical polymerization on copper electrode.
Finally, the through hole was fully filled by copper electroplating using the as-developed new formula. The hole diameter was 50 μm, the hole depth was 380 μm and the aspect ratio was 7.6. The total plating time just took 9 hours.
URI: http://hdl.handle.net/11455/3823
其他識別: U0005-1907201018302300
Appears in Collections:化學工程學系所

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