臺灣博碩士論文加值系統

本研究主要藉由一特殊化學鍍反應器，是利用反應器底部高溫加熱板加熱，反應器本體再加裝冷凝管，使整體溫度不致變高，因為局部高溫的結果，使其在界面區域產生金屬微粒，此微粒再經對流擴散吸附於基材表面，將基材表面金屬化。此方法稱之為非均溫化學析鍍。
因為此方法有一高溫熱源又有低溫冷卻產生的溫差，因此，熱效應在反應過程將扮演影響析鍍結果的角色。本研究嘗試以XRD探討在不同溫度下的銅膜晶形，進而討論非均溫化學鍍對銅膜純度的影響及其電性優劣，結果發現溫度愈高，晶形方向性愈一致，導電性及純度也愈好。此外，非均溫化學鍍除了產生微粒外，我們尚希望能夠實際應用於半導體微結構元件上，而因非均溫化學鍍又有一非線性擴散的影響，故施以添加劑在其中抑制因不良擴散而導致的孔洞缺陷結構，添加劑當中又以FS的析鍍現象較好；SPS效果不顯著，但有提高優選方向且細緻晶粒的效果；CO-890雖然有不錯的抑制效果，但效果僅於微米級結構，不適宜用於深次微米結構；PEG-1000雖然也是一常用添加劑，但在非均溫系統下，因系統析鍍速率較快，添加劑抑制效果不足，因此造成孔洞缺陷的情形嚴重。

An electroless plating reactor with specific design was used to deposit copper particles on the substrate in this study. A heating plate attached to the bottom of substrate which is fixed on the bottom of reactor and a helix cooling coil inside the reactor was arranged to precisely control the temperatures of substrate and plating bath separately. The high temperature near the surface of substrate induces the formation of metal particles, and, then, these metal particles will be deposited on substrate surface successfully. This method is named as “Non-isothermal deposition (NITD)”.
Our results show that the substrate temperature plays a detrimental role on the deposition of metal particles for this NITD process. The higher the heating temperature is, the orientation of copper film is more uniform, and the conductivity is better.
In the production of micro-structure devices for semiconductor industries, defect caused by nonlinear diffusion effect in the electroless plating reaction cannot be ignored. Therefore, effectiveness of eliminating the nonlinear diffusion effect of various surfactants are also investigated. Among the different surfactants tested, FS shows its best ability in deposition. SPS effect in reducing nonlinear diffusion phenomenon is insignificant, but the purity of copper layer is enhanced and the formed copper is fine when adding SPS in the electrolyte. CO-890 is good in production of micro-level structure, but it is not suitable in application of producing deep micro-level structure. Owing to its high deposition rate in NITD system, the inhibition ability of PEG-1000, a useful additive in electroless plating process, is not enough, leading to formation of void defect easily.

誌謝 ii
摘要 iv
ABSTRACT v
目錄 vi
表目錄 ix
圖目錄 x
1. 前言 1
2. 文獻回顧 3
2.1 半導體科技現況 3
2.2 銅導線製作目的 4
2.3 物理氣相沉積法(Physical Vapor Deposition, PVD) 7
2.4 化學氣相沉積法(Chemical Vapor Deposition, CVD) 7
2.5 電化學沉積法(Electrochemical-Deposition, ECD) 8
2.6 非均溫化學沉積法(Non-Isothermal Chemical Deposition, NITD) 17
2.7 研究動機 19
3. 實驗方法 20
3.1 實驗儀器設備 20
3.2 實驗藥品 20
3.3 基材的準備 21
3.3.1 基材之前處理 21
3.4 無電電鍍銅 22
3.4.1 界面活性劑種類與含量對液固間表面張力之影響 22
3.4.2 界面活性劑種類 23
3.4.3 界面活性劑濃度對晶種層之影響 23
3.4.4 無電電鍍銅於微結構之製備 23
3.4.5 無電電鍍銅導線之製備 24
3.5 實驗裝置 26
3.6 實驗流程 28
3.7 儀器與方法 29
3.7.1 掃描式電子顯微鏡(SEM)／(FE-SEM) 29
3.7.2 原子力顯微鏡(AFM) 29
3.7.3 表面張力測定儀(Surface Tensiometer) 29
3.7.4 X光繞射儀(X-ray Diffractometer) 30
3.7.5 四點探針(Four-Point Probe) 30
4. 結果與討論 32
4.1 非均溫無電鍍銅膜結晶性之探討 32
4.2 非均溫無電鍍銅之電性探討 38
4.3 非均溫熱效應對銅膜之影響 40
4.4 不同溫度對銅膜表面之影響 44
4.5 不同添加劑對銅膜性質之影響 49
4.6 不同添加劑之表面張力 51
4.7 不同添加劑析鍍銅膜表面粗度之影響 52
4.8 添加劑不同濃度對甲醛氧化能力之影響 57
4.9 非均溫化學鍍應用於微結構金屬化製程 60
4.10 利用非均溫系統製備晶種層再行電鍍之探討 68
5. 結論 70
6. 未來規劃 71
參考文獻 72
自傳 76

[1]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，1998。
[2]宋鈺，“非均溫化學析鍍及其在微結構製備上的應用”，博士論文，國防大學中正理工學院應用化學研究所，桃園，2003。
[3]Hong Xiao，半導體製程技術導論，培生教育出版股份有限公司，台灣，第1頁，2003。
[4]Lin Yi-Mao, Yen Shi-Chern ,“Effect of additives and chelating ag ent on electroless copper plating, ”Applied Surface Science, Vol.178, pp. 116-126, 2001.
[5]李明逵，矽元件與積體電路製程，全華科技圖書股份有限公司，台灣，第16-16- 16-17頁，2004。
[6]Lee Yong-Sun, Hong Seok-Woo, Park Jong-Wan,“Effects of heat treatment on electroless copper-deposited film in TaN diffusion barrier,”Materials Science in Semiconductor Processing, Vol.6 ,pp. 209-213, 2003.
[7]鄧經緯，“濕式活化無電鍍銅技術在TaN阻隔層上金屬化之研究”碩士論文，國立清華大學材料科學工程學系，新竹，2001
[8]Hong Xiao，半導體製程技術導論，培生教育出版股份有限公司，台灣，第477頁，2003。
[9]尤志州、劉如熹、蔡明蒔、胡淑芬、王進龍、李盈壕、呂志鵬，利用無電極鍍銅方法成長晶種層及其特性研究，毫微米通訊，第七卷，第四期，2000。
[10]Eung Jin Ahn and Jae Jeong Kim,“Additives for Superconformal Electroplating of Ag Thin Film for ULSIs,”Electrochemical and Solid state Letter, Vol.7, No.10, pp. C118-C120, 2004.
[11]Chang Shou-Yi, Lin Chi-Wei, Hsu Hong-Hui, Fang Jui-Hua, Lin Su-Jien,“Integrated Electrochemical Deposition of Copper Metallization for ULSI,” Journal of The Electrochemical Society, Vol.151 No.1 pp. C81-C88, 2004.
[12]陳世昌、沈國宏，半導體製程之金屬化銅電鍍技術，默克技術報導，21期，2003。
[13]S.D.Yosi, V.Dubin anf M.Angyal,“Electroless copper deposition for ULSI,”Thin Solid Films, Vol.262, pp. 93-103, 1995.
[14]Yuri Lantasov , Roger Palmans , Karen Maex,“New plating bath for electroless copper deposition on sputtered,”Microelectronic Engineering, Vol.50, pp. 441-447, 2000.
[15]Hiroshi Yanagimoto, Kensuke Akamatsu, Shigehito Deki, Kazuo Gotoh,“Novel Copper Electroless Plating Process on Ceramic substrate Using Copper Oxide Particles,”Electrochemical and Solid state Letter, Vol.5, No.9, pp. C87-C89, 2002.
[16]Hsu Hong-Hui, Teng Ching-Wei, Lin Su-Jien, Yeh Jien-Wei,“Sn/Pd Catalyzation and Electroless Cu Deposition on TaN Diffusion Barrier Layers, ”Journal of The Electrochemical Society, Vol.149, No.9 pp. C143-C149, 2002.
[17]Tohru Hara,Satoshi Kamijima,Yasuhiro Shimura,“Electroplating of Copper Conductive Layer on the Electroless-Plating Copper Seed Layer,” Electrochemical and Solid state Letter, Vol.6, No.1, pp. C8-C11, 2003.
[18]Zenglin WANG, Osamu YAEGASHI, Hiroyuki SAKAUE, Takayuki TAKAHAGI and Shoso SHINGUBARA,“Highly Adhesive Electroless Cu Layer Formation Using an Ultra Thin Ionized Cluster Beam (ICB)-Pd Catalytic Layer for Sub-100nm Cu Interconnections,”Jpn. J. Appl. Phys., Vol.42 pp. L1223-L1225, 2003.
[19]Liu R.S., You C.C., Tsai M.S., Hu S.F., Li Y.H., Lu C.P.,“An investigation of smooth nano-sized copper seed layers on TiN and TaSiN by new non-toxic electroless plating,”Solid State Communications, Vol.125, pp. 445-448, 2003.
[20]Tohru Hara,Kohji Sakata, Akihiro Kawaguchi, and Satoshi Kamijima,“Control of Agglomeration on Copper Seed Layer Employed in the Copper Interconnection,”Electrochemical and Solid state Letter, Vol.4, No.11, pp. C81-C84, 2001.
[21]E. WEBB,C. WITT, T. ANDRYUSCHENKO and J. REID,“Integration of thin electroless copper films in copper interconnect metallization,”Journal of Applied Electrochemistry, Vol.34, pp. 291-300, 2004.
[22]Kazuo Kondo, and Haruo Murakami,“Crystal Growth of Electrolytic Cu Foil,”Journal of The Electrochemical Society, Vol.151, No.7, pp. C514-C518, 2004.
[23]D. Josell, D. Wheeler, C. Witt, and T. P. Moffat,“Seedless Superfill: Copper Electrodeposition in Trenches with Ruthenium Barriers,”Electrochemical and Solid state Letter, Vol.6 , No.10, pp. C143-C145, 2003.
[24]N. Benouattas , A. Mosser , D. Raiser , J. Faerber , A. Bouabellou,“Behaviour of copper atoms in annealed Cu/SiOx/Si systems,”Applied Surface Science, Vol.153, pp. 79-84, 2000.
[25]V.A. Vas_ko , I. Tabakovic, S.C. Riemer, M.T. Kief,“Effect of organic additives on structure, resistivity, and room-temperature recrystallization of electrodeposited copper,”Microelectronic Engineering, Vol.75, pp. 71-77, 2004.
[26]Yosi Y. Shacham-Diamand,“Electroless Copper Deposition Using Glyoxylic Acid as Reducing Agent for Ultralarge Scale Integration Metallization,”Electrochemical and Solid-State Letters, Vol.3, No.6, pp. 279-282, 2000.
[27]周育賢，“非均溫化學鎳及銅在微結構製作之應用”，碩士論文，國防大學中正理工學院應用化學研究所，桃園，2004。
[28]Rohan Akolkar and Uziel Landauz, “A Time-Dependent Transport-Kinetics Model for Additive Interactions in Copper Interconnect Metallization”Journal of The Electrochemical Society, Vol.151, No.11, pp. C702-C711, 2004
[29]張勁燕，深次微米矽製程技術，五南圖書出版股份有限公司，台灣，第251頁，2002。