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標題: 填充矽通孔之新穎電鍍銅配方
A Novel Copper Electroplating Formula for Filling Through Silicon Vias
作者: 陳偉翔
Chen, Wei-Hsiang
關鍵字: eletroplating;電鍍;through silicon vias;copper deposition;3D chip stacking;interconection;矽通孔;銅導線;沉積銅;三維晶片堆疊
出版社: 化學工程學系所
引用: 1.Prentice-Hall, “Introduction of semiconductor Manufacturing Technology”, p.447, New Jersey, 2001. 2.P. C. Andricacos, C. Uzoh, J. O. Dukovic, J. Horkans, and H. Deligianni ,“Damascene copper electroplating for chip interconnections”, IBM Journal of Research and Devlopment., 42, 567 , 1998. 3.張勁燕, “深次微米矽製程技術”, 五南圖書出版公司, 第六章, 民國91年。 4.K. Kondo, T. Nakamura, D. Mikami, T. Ookubo “Via Filling Electrodeposition by Using Periodical-Reverse Pulse Current”, Journal of The Electrochemical Society., 6, 135, 2007. 5.J. J. Sun, K. Kondo, T, Okamura, S. Oh, M. Tomisaka, H, Yonemura, M. Hoshion, and K. Takahashi, “High-Aspect-Ratio Copper Via Filling Used for Three-Dimensional Chip Stacking,” Journal of The Electrochemical Society., 150, 355, 2003. 6.K. Kondo, T. Yonezawa, D. Mikami, T. Okubo, Y. Taguchi, K. Takahashi, and D. P. Barkey,“High-Aspect-Ratio Copper-Via-Filling for Three-Dimensional Chip Stacking”, Journal of The Electrochemical Society., 152, H173, 2000. 7.L. Xu, P. Dixit, J. miaro, J. H. L. Pang, X. Zhang, K. H. Tu, and R. Preisser “Through-wafer electroplated copper interconnect with ultrafine grains and high density of nanotwins”, Applied Physics Letters., 90, 03311, 2007. 8.P. G. Emma and E. Kursun, “Is 3D chip technology the next growth engine for performance improvement?”, IBM Journal of Research and Devlopment., 52, 541, 1998. 9.L. W. Schaper, S. L. Burkett, S. Spiesshoefer, G. V. Vangara, Z. Rahman, and S. Polamreddy,“Architectural Implications and Process Development of 3-D VLSI Z-Axis Interconnects Using Through Silicon Vias”, IEEE Transcations on Components and Packaging Technologies., 28, 3, 356, 2005. 10.ITRS Winter Conference, p23, 2007. 11.S. Das, A. Chandrakasan, and R. Reif “Timing, Engergy, and Thermal Performance of Three-Dimensional Integrated Circuits”, Great Lakes Symposium on VLSI., 338, 2004. 12.A. Rahman, A. Fan, and R. Reif, “Comparison of Key Performance Metrics in Two- and Three-Dimensional Integrated Circuits”, Interconnect Technology Conference., 18, 2000. 13.D. Banerjee, S. Souri, P. Kapur, and K. Saraswat, “3-D ICs: A Novel Chip Design for Improving Deep-Submicrometer Interconnect Performance and Systems-on-Chip Integration”, Proceedings of the IEEE., 89, 602, 2001. 14.N. T. Nguyen, E Boellaard, N. P. Pham, V. G. Kutchoukov, G. Craciun and P. M. Sarro, “Through-wafer copper electroplating for three-dimensional interconnects”, Journal of Micromechanics and Microengineering., 12, 395, 2002. 15.C. Song, Z. Wang, Q. Chen, J. Cai and L. Liu, “High aspect ratio copper through-silicon-vias for 3Dintegration”, Microelectronic Engineering., 85, 1952, 2008. 16.K. Takahashi, Y. Taguchi, M. Hoshino, K. Tanida, M. Umemoto, T. Yonezawa, and K. Kondo, “Development of Less Expensive Process Technologies for Three- Dimensional Chip Stacking with Through-Vias”, Electronics and Communications in japan., part2, 88, 7, 2005. 17.S. Spiesshoefer and L. Schaper, “IC stacking technology using fine pitch, nanoscale through silicon vias”, Electronic Components and Technology Conference., 631, 2003. 18.J. Wang, “Analytical Electrochemistry”, 2nd ed., Chapter 1, Wiley & Sons, Inc., 2000. 19.S. K. Kim, D. Josell, and T. P. Moffat, “Cationic Surfactants for the Control of Overfill Bumps in Cu Superfilling”, Journal of The Electrochemical Society, 153, C826, 2006. 20.Z. Nagy, J. P. Blaudeau, N. C. Hung, L. A. Curtiss, and D. J. Zurawski, “Chloride Ion Catalysis of the Copper Deposition Reaction”, Journal of The Electrochemical Society., 142 , L87, 1995. 21.W. P. Dow, H. S. Huang, M. Y. Yen, and H. H. Chen “Roles of Chloride Ion in Microvia Filling by Copper Electrodeposition”, Journal of The Electrochemical Society., 152, C77, 2005. 22.G. M. Brown, and G. A. Hope “A SERS study of SO42-/Cl- ion adsorption at a copper electrode in situ”, Journal of The Electrochemical Society., 405, 211, 1996. 23.N. Zukauskaite and A. Malinauskas, “Electrocatalysis by a Brightener in Copper Electrodeposition“, Sov. Electrochem., 24, 1564, 1989. 24.J. P. Healy and D. Pletcher, “The chemistry of the additives in an acid copper electroplating bath Part Ⅱ. The instability of 4, 5-dithiaoctane-1, 8-disulphonic acid in the bath on open circuit”, Journal of Electroanalytical Chemistry., 338, 167, 1992. 25.E. E. Farndon, F. C. Walsh and S. A. Campbell, “Effect of Thiourea Benzotriazole and 4,5-Dithiaoctane-1,8-Disulphonic Acid on the Kinetics of Copper Deposition from Dilute Acid Sulphate Solutions”, Journal of Applied Electrochemistry., 24, 574, 1995 26.E. Mattsson, J. O. M. Bockris, “Galvanostatic Studies of The Kinetic of Deposition and Dissolution In the Copper+Copper Sulphate System”, Transactions of the Faraday Society., 55, 1586, 1959. 27.S. N. Jeq, C. C. Wan, and Y. Y. Wang, “The influence of self-assembled disulfide additive on the pattern shape by Cu electrodeposition through mask”, Journal of Electroanalytical Chemistry., 609, 68, 2007. 28.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. 29.J. J. Kelly, A. C. West, “Copper Deposition in the Presence of Polyethylene Glycol Ⅰ. Quartz Crystal Microbalance Study”, Journal of The Electrochemical Society., 145, 3472, 1998. 30.Z. V. Feng,A. A. Gewirth, “Inhibition Due to the Interation of polyethylene Glycol, Chloride, and Copper in plating baths:A Surface Enhanced Raman Study”, Journal of Physical Chemistry., B., 107, 9415, 2003. 31.W. P. Dow, M. Y. Yen, W. B. Lin, S. W. Ho, “Influence of Molecular Weight of Polyethylene Glycol on Microvia Filling By Copper Electroplating”, Journal of The Electrochemical Society., 152, C769, 2005 32.S. C. Chang﹐J.M. Shieh﹐K.C. Lin﹐B.T. Dai﹐T.C. Wang, C.F. Chen, M.S. Feng﹐Y.H. Li , C.P. Lu﹐”Wetting effect on gap filling submicron damascene by an electrolyte” free of levelers”, Journal of Vacuum Science & Technology., B, 20, C1311, 2002. 33.方景禮,“電鍍添加劑總論”,傳勝出版社,第14章,民國85年。 34.G. K. Gomma, “Effect of azole compounds on corrosion of copper in acid medium”, Materials chemistry and physics., 56, C27, 1998. 35.J. J. Kelly and A. C. West, “Leveling of 200 nm Features by Organic Additives”, Electrochemical and Solid-State Letters., 2, C561, 1999. 36.P. Taephaisitphongse, Y. Cao, and A. C. West, “Electrochemical and Fill studies of a Multicomponent Additive Package for Copper Deposition”, Journal of The Electrochemical Society., 148, C492, 2001. 37.K. Kondo, N. Yamakawa, Z. Tanaka, and K.Hayashi, “Copper damascene electrodeposition and additives”, Journal of Electroanalytical Chemistry., 559, C137, 2003. 38.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”, Journal of The Electrochemical Society., 152, C425, 2005. 39.W. P. Dow, C.W. Liu, “Evaluating the filling performance of a copper plating formula using a simple galvanostat method”, Journal of The Electrochemical Society., 153, C190, 2006. 40.T. P. Moffat, D. Wheeler, and D. Josell, “Electrodeposition of Copper in the SPS-PEG-Cl Additive System. I. Kinetic Measurements: Influence of SPS”, Journal of The Electrochemical Society., 151, C262 ,2004. 41.D. Josell, D. Wheeler, W. H. Huber, and T. P. Moffat, “Superconformal Electrodeposition in Submicron Features”, Physical Review Letters., 4,C287, 2001. 42.T. P. Moffat, J. E. Bonevich, W. H. Huber, A. Stanishevsky, D. R. Kelly,G. R. Stafford, D.Josell, “Superconformal Electrodeposition of Copper in 500-90nm Features”, Journal of The Electrochemical Society., 147, 4524, 2000. 43.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”, Journal of Electroanalytical Chemistry., 338, C167, 1992. 44.D. Josell, D. Wheeler, W. H. Huber, J. E. Bonevich and, T. P. Moffat, “A simple Equation for Predicting Superconformal Electrodeposition in Submicronmeter Trenches”, Journal of The Electrochemical Society., 148, C767, 2001. 45.T. P. Moffat, D. Wheeler, W. H. Huber, and D. Josell, “Superconformal Electrodeposition of Copper”, Electrochemical and Solid-State Letters., 128,C26, 2001. 46.Y. Cao, P. Taephaisitphongse, R. Chalupa, and A. C. West, “Three-Additive Model of Superfilling of Copper”, Journal of The Electrochemical Society., 148, C446, 2001. 47.A. C. West, “Theory of Filling of High-Aspect Ratio Trenches and Vias in Presence of Additive”, Journal of The Electrochemical Society., 147, 227, 2000. 48.A. C. West, S. Mayer, and J. Reid, “A Superfilling Model that Predicts Bump Formation”, Electrochemical and Solid-State Letters., 4, C50, 2001. 49.胡啟章,“電化學原理與方法”,五南圖書出版股份有限公司,民國92年。 50.汪建民,“材料分析”,中國材料科學學會,民國九十年。 51.林敬二、林宗義譯,“儀器分析”,美亞書版股份有限公司,民國八十三年 52.黃河樹,碩士論文, “有機添加劑對電鍍同填充IC機版微米級盲孔之反應機制研究”,國立雲林科技大學,民國九十二年。 53.蘇勇誌,碩士論文, “平整劑與加速劑在印刷電路板製程中對填孔電鍍的影響”,國立雲林科技大學,民國九十二年。 54.Y. B. Li, W. Wang, and Y. L. Li, “Adsorption Behavior and Related Mechanism of Janus Green B during Copper Via-Filling Process”, Journal of The Electrochemical Society., 156(4), D119, 2009. 55.B. H. Cho, J. J. Yun, and W. J Lee, “Filling of Very Fine Via Holes for Therr-Dimensional Packaging by Using Ionized Metal Plasma Sputtering and Electroplating”, Journal of Applied Physics., 46, No.46, pp.L1135-1137, 2007. 56.陳祥豪,碩士論文, “填充微米及導孔與通孔之電鍍銅配方研究”,國立雲林科技大學,民國九十三年。 57.劉德輝,碩士論文, “新穎平整劑的開發及應用於電鍍銅填充盲、通孔”,國立中興大學,民國九十七年。 58.R. Akolkar and U. Landau, “Mechanistic Analysis of the “Bottom-Up” Fill in Copper Interconnect Metallization”, Journal of The Electrochemical Society., 156, D351, 2009 59.Q. Huang, B. C. Baker-O’Neal, J. J. Kelly, P. Broekmann, A. Wirth, C. Emnet, M. Martin, M. Hahn, A. Wagner, and D. Mayer, “Suppressor Effects during Copper Superfilling of Sub-100nm Lines”, Electrochemical and Solid-State Letters., 12, D27, 2009. 60.O. Magnussen, “Ordered Anion Adlayers on Metal Electrode Surfaces”, Chemical Reviews., 102, 607 (2002). 61.W. P. Dow, H. H. Chen, M. Y. Yen, and C. W. Liu, “Simultaneous Filling of Microvias and Through Holes by Copper Electroplating for High Density Interconnection of PCB”, ECS Transactions, 2, 259, 2007. 62.K. Kondo, T. Matsumoto, and K. Watanabe, “Role of Additives for Copper Damascene Electrodepostion Experimental Study on Inhibition and Acceleration Effects”, Journal of The Electrochemical Society., 151, C250, 2004. 63.K. Umemoto, “Electrochemical Studies of the Reduction Mechanism of Tetrazolium Salts and Formazans”, The Chemical Society of Japan., 62, 3783, 1989. 64.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, 2004
為了追求日新月異的科技,將產品微小化、製作成本降低以及效能提升持續在進行,相關的研究也因此而持續在發展,能將以上目標完成的3D晶片堆疊技術因此而被開發。本論文的研究目的是希望能將在3D晶片堆疊技術不可或缺的矽通孔(Through Silicon Vias, TSV)以電鍍的方式完全充塞銅在其中,促使3D晶片堆疊技術的開發。
為了填充銅於高深寬比的矽通孔內,以往用在印刷電路板的電鍍添加劑已不堪使用,因此吾人先利用電化學分析方法初步挑選出一些新穎之電鍍添加劑,將其分別以單劑與多劑的電鍍填孔方試進行電鍍,找出其適當的電鍍方式及參數。吾人分別找出適用於多劑的平整劑並命名為TTC,而適用於單劑的平整劑為TV。當TTC運用於多劑配方電鍍填孔,除了能使孔完全充塞銅,更能在填孔的同時使銅以平台方式沉積於孔內,降低孔洞與縫隙的產生。經過篩選與測試後吾人發現TV適合以單劑填孔電鍍方式使銅沉積於孔內,除此之外也發現使用此配方能造成板面不沉積銅,降低後續利用化學機械研磨(Chemical Mechanical Polishing, CMP)去除的負擔並降低製作成本。

The development of modern science and technology proceeds quicker and quicker. Three-dimensional (3D) integration of chips is fast growing to carry out high-speed performance and high-density packaging. 3D integration uses through-silicon-vias (TSVs) to interconnect multiple active circuit layer in a single chip, that performs high density interconnects with a small form factor. This thesis achieves void-free TSV filling using electrochemical deposition (ECD) of copper, because a void formed in the TSV may cause serious reliability issues.
Since the aspect ratio of the TSV is much higher than that of the vias of printed circuit boards (PCBs), a common copper plating formula for PCBs cannot fully fill the TSV with copper deposit. In this thesis, some novel organic additives were screened by chronopotentiometry to be levelers. Electroanalytical measurements and feature-filling experiments were carried out to study the effect of these additives.
Copper electroplating formulas with multi-component and with single component for TSV filling were developed. TTC is a new additive, which is appropriate for TSV filling in multi-component method. A trapezium-type profile of the top copper deposit in the filled TSV was achievable using the plating formula with TTC. This plating process can make sure of no void and seam formation during plating. TV was a novel additive for filling TSV in a single component system. Surprisingly, the thickness of copper on the wafer surface was a constant during the plating process, indicating that the copper deposition is highly selective. The high selectivity of copper fill greatly reduces the loading of chemical mechanical polishing (CMP) and saves the process time of TSV.
The insulating layer, barrier layer and copper seed layer were formed inside the TSV before copper electrodeposition. However, the step coverage of sputtered copper seed layer was not good enough. A void-free filling of the TSV is not only achieved by an excellent plating formula but also by good continuity and conformality of the seed layer. The thickness of the seed layer coated on the via wall has significant effect on the TSV filling. If the seed layer is not continuous, then a void-free filling of the TSV is not achievable. In this work, we developed another plating formula to repair the discontinuous seed layer rendering it to be continuous and conformal. Thus, the TSV with a high aspect ratio were fully filled after repairing the seed layer using the special plating formula.
其他識別: U0005-2407200915511700
Appears in Collections:化學工程學系所

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