臺灣博碩士論文加值系統

本研究以快速且簡易的新型監測方法簡化定量傳統較複雜的添加劑含量分析程序。以高銅低酸做為基礎電鍍母液，並添加Cl-、MPSA、PEG、2-MP、JGB等添加劑，利用電化學分析儀做循環線性掃描伏安法(CLSV)與定電位分析觀察添加劑的吸附行為、協合效應、抑制效應，以及穩定性。電鍍後之晶片再以表面輪廓儀(α-step)、掃描式電子顯微鏡(SEM)分析晶片表面鍍層和孔洞鍍層之填滿型態來對照快速電流差定量法。實驗結果顯示，在-0.23V下，添加MPSA含量到5ppm時，能夠有效的增加電鍍所需的電流量，當添加MPSA超過5ppm時則反而可能形成多餘阻障層抑制銅離子沉積但其電流量還是比母液大。在長時間的電鍍中，可利用添加劑對流吸附(CDA)的原理，利用定電壓(-0.23V)方式分析比較添加各種配方來快速監測不同添加劑濃度的電流密度差值，以得知鍍液中添加劑濃度是否足夠，並利用此電流差值定量方法快速簡易驗証監測晶片沉積填滿形態。相同原理也可適用於其他添加劑的部份。經由實體電鍍的結果可以確切的了解當某種添加劑不足時，所呈現的表面形態以及剖面形態各個不同。

In this study, a new type of rapid and easy method simplify the quantitative of traditional analysis procedures of additives. we use copper plating recipes of acid cupric sulfate containing additives mixtures. The additives are used for electroplating which were chloride ion (Cl-), sodium 3-mercapto-1-propanesulfonate (MPSA), polyethylene glycol (PEG), 2-mercaptopyridine (2-MP), and janus green B (JGB). Additionally, the copper deposition behavior from electroplating copper recipes containing various additives were investigated by cyclic linear sweep voltamme¬try (CLSV) and potentiostatic measurements (PM). The thickness of films were measured by profilometer and the morphology was analyzed by Scanning Electron Microscope(SEM). Ring Disk Electrode(RDE) experimental results showed that the current density of plating increased with increasing the content of MPSA to maximum current density up to 5 ppm at -0.23V. The calibration curve (current density difference-concentration) results indicated the rapidly quantitative method of monitoring additives of copper electroplating replacing the conventional method. It is shown that the morphology of the deposition film depends on the additive concentration and the deposition position of holes.

目錄
摘要 I
ABSTRACT II
目錄 III
表目錄 VI
圖目錄 VII
第一章 緒論 1
第二章 文獻回顧 6
2.1 電子構裝技術發展 6
2.1.1 半導體元件構裝技術的定義 7
2.1.2 半導體元件構裝技術的功能 7
2.1.3 半導體元件構裝技術的演變 9
2.2 金屬化製程及導線材料 13
2.2.1 金屬化製程 13
2.2.2 金屬薄膜的沉積之比較 16
2.2.3 銅製程之興起 17
2.2.4 介電層與銅擴散阻障層 19
2.3 電鍍 20
2.3.1 電鍍的原理 21
2.3.2 極化作用 22
2.3.3 氫氣反應 24
2.3.4 金屬銅電鍍 27
2.4 電鍍液的組成 28
2.4.1 氫離子(H+) 31
2.4.2 氯離子(Cl-) 31
2.4.3 光澤劑(Brighteners) 32
2.4.4 抑制劑(Suppressor) 32
2.4.5 平整劑(Leveler) 32
2.5 反應速率常數方程式 33
2.6 鍍液中添加劑的檢測方法 34
2.6.1 循環伏安剝除法(CVS) 35
2.6.2 液相層析(LC) 35
第三章 實驗 36
3.1. 實驗藥品與儀器 36
3.1.1 實驗藥品 36
3.1.2 實驗儀器 37
3.2. 實驗步驟 37
3.2.1 電化學分析 38
3.2.1.1 循環線性掃描伏安法 39
3.2.1.2 定電壓分析之研究 39
3.2.2 電化學電鍍銅實驗 41
3.2.2.1 添加劑對於晶片電鍍銅表面鍍層之分析 41
3.2.2.2 添加劑對於晶片電鍍銅之微孔鍍層分析 44
3.3 理論厚度計算 46
3.4 相對沈積厚度 46

第四章 結果與討論 47
4.1 母液和添加劑之電化學行為分析 47
4.1.1 母液之分析 49
4.1.2 不同酸性及濃度之分析 51
4.1.2.1 高銅母液 51
4.1.2.2 低銅母液 56
4.1.3 氯離子濃度及轉速 61
4.1.4 光澤劑濃度及轉速之分析 63
4.1.5 平整劑濃度及轉速之分析 71
4.2 定電位下快速定量模擬分析及動力學之分析 73
4.2.1 MPSA定量分析 75
4.2.2 平整劑分析 79
4.2.2.1 2-MP之濃度分析 79
4.2.2.2 JGB之濃度分析 85
4.2.3 聚乙二醇(PEG) 定量分析 90
4.3 晶片微電鍍鍍層性質分析 96
4.3.1 晶片表面形態(Morphology)分析 97
4.3.2 晶片剖面型態分析 100
第五章 結論與未來展望 106
5.1 結論 106
5.2未來展望 107
第六章 參考文獻 108

[1]H. Xiao, “Introduction to 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. Develop 42, 567-574(1998).
[3]邱顯光、蔡明蒔、林鴻志, “雙鑲嵌結構製作技術簡介”，奈米通訊，第六卷，第三期(1999).
[4]F. E. Stone,G. O. Mallory, J. B. Hajdu, “Electroless plating: Fundamentals and Application”, Editors, American Electroplaters and Surface Finishers Society, 331, Florida(1990).
[5] H. Akahoshi, M. Kawamoto, T. Itabashi, O. Miura, A. Takahashi, S. Kobayashi, M. Miyazaki, T. Mouth, M. Wajima, T. Ishinaru, “Fine Line Circuit Manufacturing Technology with Electroless Copper Plating”, IEEE Trans. Comp. Pack. Manufact. Technol. 18, 127 - 135 (1995).
[6] M. T. Bohr, International Electron Devices Meeting, p.241 (1995).
[7] Denny Thiemig, Ronny Lange, Andreas Bund, Electrochimica Acta 52, 7362 - 7371 (2007).
[8]F. A. Harraz, T. Sakka, Y. H. Ogata, Electrochimica Acta 47, 1249-1257 (2002).
[9]K. Kondo, N. Yamakawa, Z. Tanaka, K. Hayashi, “Copper Damascene Electrodeposition and Additives”, Journal of Electroanalytical Chemistry 559, 137 - 142 (2003).
[10] Y. L. Kao, G. C. Tu, C. A. Huang, J. H. Chang, Materials Science and Engineering A382, 104 - 111 (2004).
[11]竇維平、黃河樹、蘇勇誌、顏銘瑤，“電鍍銅添加劑在IC及IC構裝機板上的應用”，化工專刊，第50卷，第4期 (2003)。
[12]M. Georgiadou, D. Veyret, R. L. Sani, R. C. Alkire, “Simulation of Shape Evolution During Electrodeposition of Copper in The Presence of Additive”, J. Electrochemical Soc. 148, C54 - C58 (2001).
[13]Shuhei Miura, Hideo Honma, “Advanced Copper Electroplating for Application of Electronics”, Surface and Coatings Technology 169 - 170 (2003).
[14]田民波/著、顏怡文/教訂, “半導體電子元件構裝技術”(2005).
[15]L. Zan, Z. Liu, Z. Yang, and Z. Wang, “A synergy effect of 2-MBT and PE-3650 on the bottom-up filling in electroless copper plating”, Electrochemical and Solid-State Letters 14, D107-D109(2011).
[16]張鼎張、劉柏村，“NDL在無機類低介電常數材質的研發簡介”，奈米通訊，第五卷，第四期。
[17]莊達人,“VLSI 製造技術”，高立出版社 (1999)。
[18]張勁燕, “電子材料”, 五南圖書出版股份有限公司 (2009).
[19]王裕文, “先進電子構裝中的盲孔用電鍍銅來填滿之研究”, 國立聯合大學化學工程系碩士論文(2008).
[20]楊正杰、張鼎張、鄭晃忠， “銅金屬與低介電常數材料與製程”，毫微奈米通訊，第七期，第四卷。.
[21]吳世全,“銅金屬導線之發展與研製評估”,奈米通訊，第五卷，第三期。
[22]C. A. Chang, Appl. Phys. Lett.57,p. 617 (1990).
[23]J. S. H. Cho, EKE EDM Technical Digest 265 (1993).
[24] Y. Shacham Diamand, J. Electrochem. Soc.140, p.2427 (1993).
[25]J. Palleau, in Advanced Metallization for Devices and Circuits- science, Technology and Manufacturability, edit by S. P. Muraka, Materials research Society, Pittsburgh, PS, p.225 (1994).
[26]D. Adams, Advanced Metallization for Devices and Circuits- science, Technology and Manufacturability, edit by S. P. Muraka, Materials research Society, Pittsburgh, PS, p.231 (1994).
[27] C.-K. Hu, Thin Solid Films 262,p. 84 (1995).
[28]A. V. Gelatos, Tech. Dig. of VLSI Symposium on Technology, 25 (1995).
[29] H. Ono, Appl. Phys. Lett.64, p.1511 (1994)..
[30]J. O. Olowolafe, J. Appl. Phys.72, p.4099 (1992).
[31]劉柏村、張鼎張，“低介電常數材料應用於導體連線製程技術的探討”,奈米通訊，第九卷，第二期。
[32]A. J. Bard, L. R. Faulkner, “Electrochemical Methods Fundamentals and Applications”, John Wiley & Sons, Inc..
[33]田福助，“電化學原理與應用”，高立圖書有限公司 (1996)。
[34]M. Jurkiewecz-Herbich, Electrochim Acta 47, 2429 (2002).
[35] 方景禮，“電鍍添加劑總論”，傳勝出版社 (1996)。
[36]張鼎張、胡榮治、陳力俊，“具有Super-filling現象的電鍍銅技術與其在超大型積體電路中的應用”，奈米通訊，第六卷，第四期 (1999)。
[37]Chien-Hung Chen, Chun-Wei Lu, Su-Mei Huang, Wei-Ping Dow, “Effects of Supporting Electrolytes on Copper Electroplating for Filling Through-hole” , Electrochimica Acta 56, 5954 - 5960 (2011).
[38]P. Taephaisitphongse, Y. g Cao, A. C. West, “Electrochemical and Fill Studies of A Multicomponent Additive Package for Copper Deposition”, J. Electrochem. Soc. 148, C492 - C497 (2001).
[39]B. Wohlmann, Z. Park, M. lKruft, C. Stuhlmann, K. Wandelt, “An In-situ and Ex-situ Study of Chloride Adsorption on Cu(111) Electrodes in Dilute HCL Solutions”, Colloids and Surfaces A 134, 15 - 19 (1998).
[40]P. M. Vereecken, R. A. Binstead, H. Deligianni, P. C. Andricacos ”The Chemistry of Additives in Damascene Copper Plating”, IBM J. RES. & DEV., Vol.49, No.1 (2005).
[41]Wei-Ping Dow, Her-Shu Huang, “Roles of Chloride Ion in Microvia Filling by Copper Electrodoposition ”, Journal of The Electrochemical Society 152(2), C67 - C76 (2005).
[42]V. Annamalai, J.B. Hiskey, L.E. Murr, Hydrometallurgy 3, 163 (1978).
[43]Wei. Ping. Dow, Her.Shu. 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 Society152, C425-C434 (2005).
[44] The Fundamentals of Cyclic Voltammetric Stripping, Application Note, ECI Technology Inc..
[45]Wei-Ping Dow, Ming-Yao Yen, Sian-Zong Liao, Yong-Da Chiu, Hsiao-Chun Huang, “Filling Mechanism in Microvia Metallization by Copper Electroplating”, Electrochimica Acta 53, 8228 - 8237 (2008).
[46] Yu-Ao Jiang, Ai-De Zhang, Li-Bing Liu, Yu Du, Nai-Kui Gao, Zong-Ren Peng, “Study of Predicting Breakdown Voltage of Stator Insulation in Generator Based on BP Neural Network”, Academic Journal of Xi'an Jiaotong University 19(1), 34 -37 (2007).
[47]Chien-Hung Chen, Chun-Wei Lu, Su-Mei Huang, Wei-Ping Dow, “Effects of Supporting Electrolytes on Copper Electroplating for Filling Through-hole” , Electrochimica Acta 56, 5954 - 5960 (2011).
[48]M. Yokoi, S. Konishi, T. Hayashi, “Adsorption Behavior of Polyoxyenthyleneglycol on The Copper Surface in An Acid Copper Sulphate Bath”, Denki Kagaku 52, 218 - 223 (1984).