臺灣博碩士論文加值系統

在積體電路的金屬化製程中，銅因為有較低的電阻值與較佳的抗電子遷移特性，因此被用來取代鋁合金做為內連線材料。目前商業上的銅製程大都採用電鍍法，但是此方式需要黏著層及高品質的晶種層。如果使用化學鍍銅，則其所需的成本遠比其他方式低，如化學氣相沈積或物理蒸鍍。
這篇論文主要針對不同添加劑對化學銅析鍍影響之研究。化學鍍銅的應用廣泛，而鍍層結構的良窳，以及鍍液的穩定性，主要是依靠添加劑的作用。當鍍浴加入各種添加劑後，對化學鍍銅鍍層之析鍍速率、表面形態、結晶結構、組成分、電阻率之影響。利用XRD與SEM觀察鍍層的結晶情形及鍍層表面形態。
化學鍍銅過程中，甲醛的氧化反應會釋出氫氣，其會影響鍍浴的穩定性。因此良好的攪拌方式，可以快速去除氫氣，進而改善膜厚分佈以及鍍浴穩定性等多項優點。一般常見的攪拌方法：( 1 ) 空氣攪拌( 2 ) 超音波震盪( 3 ) 工件移動（陰極擺動）。
交流阻抗技術在電化學的應用相當廣泛，例如腐蝕工程、半導體、電池工業，電鍍程序和電化合成等方面，最主要它可提供一些反應動力學和反應機構上的訊息。本文利用電化學阻抗光譜（electrochemical impedance spectroscopy, EIS）來研討添加劑2-mercaptobenzothiazole影響化學鍍銅析鍍之機制，並模擬求出以銅為工作電極之電化學電解之等效電子電路圖。研究發現在含有添加劑之化學鍍銅鍍液中，以銅為工作電極之電雙層電荷轉移阻抗值 與電容值 都有增加。

Copper is replacing aluminum as the advanced ULSI interconnect material because
of its lower resistivity and better electromigration performance. Currently in the ULSI
industry, copper is deposited by electroplating. But an adhesion/barrier layer and
high-quality seed layer is required. Electroless copper plating offers the advantages of
lower cost relative to other techniques such as CVD and PVD.
In this thesis, Electroless copper deposition effects on electroless plating with two
additives, 2-mercaptobenzothiazole and Potassium iodide, were studied and reported.
Electroless copper deposition is used widely in pratice. The properties of deposits and
the stability of plating solution depend most on the effect of the additives. When
additives have been added, they not only increase charge transfer resistance and
apparent activation energy but also produce a smooth coating that has a finer and
smaller grain structure than that without grain refiners. The element analyses of
deposition were explored via X-ray diffraction (XRD) and X-ray photoelectron
spectroscope (XPS), respectively.
AC impedance measurement, when applied to the study of electrochemical systems,
can provide a wealth of kinetic and mechani- stic information. The technique is
becoming popular for the study of corrosion engineering, semiconductors, battery
industries, electroplating process and electro-organic synthesis.
These results show that with addition of 2-mercaptobenzothiazole as additive
the borate buffered electroless copper plating solutions was stabilized and the plating
rate was decreased from 14.68 μm hr to 5.860 μm hr with addition of 20
iii
mg L 2,2’-Dipyridine, surface morphology of copper deposition was smoothed, the
texture coefficient remained the same within experimental error, the size of the
crystal was decreased, the oxygen content of copper deposition was decreased, the
resistivity was decreased from 51.49μΩ − cm to 6.83μΩ − cm with addition of 20
mg L 2-mercaptobenzothiazole in plating solution.The charge transfer resistance
and double layer capacitance of the working electrode were increased.

中文摘要 i
英文摘要 ii
誌謝 iv
目錄 v
表目錄 vii
圖目錄 viii
第一章 緒論 1
1.1 前言 1
1.2 研究動機與本文大綱 5
第二章 原理與文獻回顧 7
2.1化學鍍原理 7
2.2化學鍍銅之反應式及反應機制 9
2.2.1 化學鍍銅之反應式 9
2.2.2 反應機制 10
2.3鍍浴組成及特性 12
2.4鍍浴之攪拌方式 15
2.4.1 空氣攪拌 15
2.4.2 陰極擺動 16
2.4.3 超音波震盪器 16
2.4鍍浴之攪拌方式 15
2.4.1 空氣攪拌 15
2.4.2 陰極擺動 16
2.5化學鍍銅之活化處理 18
2.4.1 空氣攪拌 15
2.4.2 陰極擺動 16
2.6添加劑的效應 20
2.7交流阻抗分析 21
2.7.1 交流阻抗光譜原理 21
2.7.2 交流阻抗光譜的基本解析圖 25
第三章 實驗方法 29
3.1實驗藥品 29
3.2基材 30
3.3基材之前處理 31
3.3.1 前處理配方 31
3.3.2 前處理之作用及目的 31
3.4鍍浴之配方 33
3.5化學銅析鍍攪拌方式 34
3.6化學銅析鍍實驗步驟 35
3.6.1 基材前處理流程 35
3.3.2 化學銅析鍍之流程圖 36
3.7銅層性質分析 37
3.7.1 分析儀器及其量測原理 37
3.7.1.1 掃描式電子顯微鏡 37
3.7.1.2 四點探針電阻率量測儀 38
3.7.1.3 X-ray螢光測厚儀 39
3.8交流阻抗光譜儀之實驗方法 40
3.8.1 鍍浴之配方 40
3.8.2 實驗步驟 41
3.8.2.1 交流阻抗光譜之各項操作條件 41
3.8.2.2 交流阻抗光譜操作程序 42
第四章 結果與討論 43
4.1不同添加劑對析鍍速率及鍍層厚度之影響 43
4.1.1 重量分析法 43
4.1.2 儀器量測法 48
4.2鍍層之電阻分析 55
4.3鍍層表面形態之分析 59
4.3.1 不同攪拌方式之表面形態 59
4.3.2 不同添加劑對化學銅鍍層之表面形態 60
4.4交流阻抗光譜之探討 73
4.4.1 奈奎斯特圖 (Nyquist plot) 73
4.4.2 波特圖 (Bode plot) 74
4.4.3 等效電路模擬圖 75
第五章 結論 78
第六章 參考文獻 80

[1]R. A. Levy, M. L. Green and P. K. Gallager, “Characterization of LPCVD Aluminum for VLSI process,” J. Electrochem. Soc., 1984, p.2175.
[2]C. H. Ting, Conference Program and Abstracts, Advanced Metdlization for ULSI　Applications Conference, 1994, P. 517.
[3]楊正杰，張鼎張，鄭晃忠，“銅金屬與低介電常數材料與製程”，毫微米通訊，第七捲，第四期，2000
[4]鄭俊麟，“探討半導體金屬化製程之金屬鉭薄膜的沉積與化學添加計對銅沉積之影響”，碩士論文，私立中圓大學化學工程研究所，桃園，第3頁，2002。
[5]Whitman, C., Moslehi, M. M., Paranjpe, Velo, A. L., and Omstead, T., “Ultra Large Scale Integrated Metallization and Interconnects,”J. Vac. Sci. Technol. A, Vol. 17, pp. 1893-1897, 1999.
[6]R. Kroger, M. Eizenberg, D. Cong, N. Yoshida, L.Y.Chen, S. Ramaswami, and D.Carl, J. Electrochem. Soc., 146, 3248(1999)
[7]S..K. Koh, S.C Choi, K.H. Kim, H.-J. Jung, G.J. Choi,H.S.Yang, and Y.S. Cho,Thin Solid Films, 347,121(1999)
[8]E.C. Cooney III, D.C. Strippe, and J.W. korejwa, J. Vac. Sci. Technol. A, 18, 1550(2000).
[9]S.M. Rossnagel, and J. Hopwood, J. Vac. Sci. Technol,B, 12, 449(1994).
[10]N. Motegi, Y. Kashimoto, K. Nagotani, S. Takahashi, T.Kondo, Y. Misuzawa, and I. Nakayama, J. Vac. Sci. Technol. B, 13, 1906(1995).
[11]L.J Friedrich, S.K. Dew, M.J. Brett, and T.Smy, J. Vac.Sci. Technol. B, 17, 186(1999).
[12]M. Georgiadow, D. Veyret, R.L. Sani, and R.C. Alkire,J .Electrochem. Soc., 148,C54(2001).


[13]W.C. Gau, T.C. Chang, Y.S.Lin, J.C.Hu , L.J.Chen, C.Y.Chang, and C.L.Cheng, J.Vac. Sci. Technol.A, 18,656(2000)
[14]S.-Y.Chiu, J.-M.Shieh, S.-C Chang, K.-C Lin, B.-T.Dai,C.-F.chen, and M.- S. Feng, J. Vac. Sci. Technol B, 18,2835(2000).
[15]W.-T. Tseng, C.-H. Lo, S.-C. Lee, J. Electrochem. Soc., 148, C327(2001).
[16]W.-T. Tseng, C.-H. Lo, S.-C. Lee, J. Electrochem. Soc., 148, C333(2001).
[17]S. Q. Wang, “Filling of Contacts and Interconnects with Cu by XeCl Laser Reflow,” VMIC Conference, Santa Clara, June, 1990, pp.431-434.
[18]尤志州，半導體製程之無電極鍍銅成長晶種層特性研究，碩士論文，國立臺灣大學化學研究所，台北，2000。
[19]D.W.Wabner, Chr.Petrov and J.Hofmann, Matalloberflaeche, 26,p362(1972); 27, p383(1973).
[20]J.Kim, S.H.Wen, D.Y.Jung and R.W.Johnson, IBM J.Res.Develop.,28. pp697-709(1984)
[21]Microelectronic Packaging Handbook, Eds. R.R.Tummula and E.j. Rymaszewski (Van Nostrand Reinhold, N.Y,(1989)
[22]C.A.Deckert. ”Electroless Copper Plating A Review: Part 1”, Plating and surface Finishing, Vol.82,Iss.2,p48(1995)
[23]逢板哲爾,“化學反應製造金屬薄膜,”表面處理工業雜誌,3期（1986）25-31
[24]H. Narcus, Metal Finishing 45 (1947) 64
[25]A.E. Cahill, American Electrochemical Society Proceedings 44(1957) p130.
[26]R.J. Zeblisky, J.F. McCormack, J.D. Williamson, F.W. Shneble,U.S. Patent 3,095,309 (1963).
[27]Aina Hung, "Electroless Copper Deposition with Hypophosphite as Reducing Agent," Plating and Surface Finishing,Vol.75, No.1, pp.62-65, 1988
[28]Pei-Chi Yen, "Improved ABS plastic activating treatment for electroless copper plating," Polymer Communications, vol. 36, no. 17, 1995, pp.3399-3400.


[29]L. G. Bhatgadde, S. Joseph, S. C. Kulkarni, "Electroless copper/nickel/gold plating of ferrite substrates," Metal Finishing, april, 1996, pp. 45-51.
[30]D. H. Cheng, W. Y. Xu, Z. Y. Zhang and Z. H. Yiao, "Electroless copper plating using hypophosphite as reducing agent," Metal Finishing, January, 1997, pp.34-37.
[31]Y. S. Dimand, S. Lopatin, "High aspect ratio quarter-micron electroless copper integrated technology," Microelectronic Engineering, vol. 37, no. 38, 1997, pp.77-88.
[32]H. Oita, M. Matsuoka and C. Iwakura, "Deposition rate and morphology of electroless copper film from solutions containing 2,2''-dipyridyl," Electrochimica Acta, vol. 42, no. 9, (1997), pp. 1435-1400.
[33]Y. S. Diamand, V. M. Dubin, M. Angyal "Electroless Copper deposition for ULSI ," Thin Solid Films 262(1995 ) pp. 93-103.
[34]W. H. Lin, H. F. Chang, "Effect of chelating agents on the structure of electroless copper coating on alumina power" Surface and Coatings Technology, no. 107,1998, pp. 48-54.
[35]D. T. Hsu, F. G. Shi, S. Lopatin, Y. S. Diamand, B. Zhao, M. Brongo, P. K. Vasudev, "Electroless copper deposition solution induced chemical changes in low-k fluorinated dielectrics," Materials Science in Semiconductor Processing,no.2, 1999, pp. 19-22.
[36]Y. A. Yang, Y. B. Wei, B. H. Loo, J. N. Yao, "Electroless copper plating on a glass subatrate coated with ZnO film under UV illumination," Journal of Electroanalytical Chemistry, no. 462, 1999, pp. 259-263.
[37]H. Honma, "Via-filling using electroplating for build-up PCBs" Electrochimica Acta, 47, 2001, pp.85-89.
[38]R. S. Liu, C. C. You, M. S. Tsai, S. F. Hu, Y. H. Li, C. P. Lu, "An inverstigation of smooth nano-sized copper seed layers on TiN and TaSiN by new non-toxic electroless plating," Solid State Communications, no. 125, 2003, pp. 445-448.

[39]J. Bielinski and K. kamiinnski, Surf. And Coat. Tech., 31, 223, 1987.
[40]G. O. Mallory and J. B. Hajdu, Editors, “Electroless Plating, Fundamentals and Application”, American Electroplating and Surface Finishiners Society, Orlando, Florida (1990).
[41]D.R.Ferrier,U.S.P.,4.325.990,1982
[42]Vaskelis A., Stalnionis G.., Jusys Z., “Cyclic voltammetry and quartz crystal microgravimetry study of autocatalytic copper(Ⅱ) reduction by cobalt(Ⅱ) in Ethylenediamine solutions,”Journal of Electroanalytical Chemistry, Vol465, pp. 142-152,1999.
[43]周榮廷，“化學銅溶液穩定性問題的探討”，表面技術雜誌，廣西，第121期，1990。
[44]Yosi, S.D.,Dubin, V. and Angyal, M.,“Electroless copper deposition for ULSI,”Thin Solid Films, Vol.262, pp.93-103, 1995.
[45]謝朝全，置換活化法在Ta(N)/SiO2/Si基材上無電鍍銅膜之研究，碩士論文，國立清華大學，新竹，1999。
[46]Jeff Hancick. Blue Wave Ultrasonic. Reprinted from ASM Handbook Volume 5：Surface Engineer.
[47]黃先輝，“應用超音波攪拌對電鍍銅的電化學行為之探討”，碩士論文，國立台北科技大學，台北，2004。
[48]A. Amirudin and D. Thierry, Progress in Organic Coatings, no. 26, 1995, pp. 1-28.
[49]J. R. Macdonald, "Impedance Spectroscopy," John Wiley & Sons, 1987.
[50]林漢棠，以交流阻抗技術研究有機與鋅粉塗料之行為，碩士論文，元智大學化學工程研究所，桃園，2001。