臺灣博碩士論文加值系統

本研究利用非均溫化學析鍍法（Non-Isothermal Deposition, NITD）製備鎳鉬磷合金奈米薄膜，藉由非均溫高溫系統對於化學鍍鎳具有較大的反應驅動力，可讓鍍液中鎳離子還原，產生大量的鎳鉬磷合金奈米微粒，並在半導體元件表面析鍍ㄧ層鎳鉬磷合金奈米薄膜，以作為大馬士革銅製程所需的擴散障礙層。研究中以鍍液組成、pH值、操作溫度、析鍍時間與鉬酸鈉濃度作為操作參數，分別探討鎳磷合金奈米核點之表面形態、鎳磷合金奈米薄膜表面粗糙度、薄膜結構、薄膜之電性以及添加不同鉬酸鈉濃度後對次磷酸根氧化電流之變化。
研究結果顯示，在高溫析鍍時可驅使大量的鎳磷合金奈米微粒形成；且隨析鍍溫度提升，鎳磷合金奈米成核量越多，致使微粒粒徑相對縮小，可形成較薄的阻障層。反之，若以低溫析鍍，鎳磷合金成核量少，形成的金屬微粒，則形成較厚之鎳磷合金金屬鍍層。而鉬酸鈉的添加可以增加鍍層熱穩定，減少鎳-磷合金鍍層應力產生，並且有效的抑制成核後金屬微粒的成長，使金屬奈米鍍層厚度更薄，因此可得到一鎳鉬磷合金奈米薄膜。

This thesis aims to study the deposition of Ni-Mo-P nano-thin-film on silicone wafer using non-isothermal deposition (NITD) method. The higher deposition temperature in the NITD method provides higher driving force to directly reduce the electrolyte to the Ni-Mo-P nano-particles without using of any noble metal as catalyst. These nano-particles finally grew to form a nano-scale thin film, which can act as a barrier layer in the copper Damascene process of IC semiconductor industry. The effects of operating parameters, such as the composition of electrolyte, the PH value of electrolyte、the deposition temperature、the concentration of NiSO4 and Na2MoO4, and the deposition time, on the morphology of deposited particles, the surface toughness, microstructure and sheet resistivity of deposited films were studied. The Cyclic Voltammetry was also used to analyze the effect of MoO42- on the deposition current.
The result shows that there was a great quantity of nano particles forming in the NITD process. The higher deposition temperature resulted in a greater amount of Ni-Mo-P nano-particles and smaller mean size of these particles, which eventually grew to a thinner deposition film. On the contrary, the lower deposition temperature resulted in a lesser amount of Ni-Mo-P particles and larger mean size of these particles, which eventually grew to a thicker deposition film. The adding of Na2MoO4 can increase the thermal stable of the deposition film, reduce the residual stress of Ni films and alloy and inhibit the coarsening of Ni-Mo-P nucleus to reduce the thickness of deposition film to nano-scale.

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 v
圖目錄 viii
表目錄 xi
1.前言 1
2.文獻回顧 3
2.1積體電路現況 3
2.2阻障層製作目的 7
2.2.1阻障層沉積技術 8
2.2.1.1物理氣相沉積法(Physical Vapor Deposition, PVD) 8
2.2.1.2有機金屬化學氣相沉積法(Metalorganic Chemical Vapor Deposition, Mo-CVD) 8
2.2.1.3原子層沉積(Atomic layer deposition, ALD) 9
2.3化學鍍 10
2.3.1化學鍍原理 10
2.3.2化學鍍鎳之反應機制 11
2.3.2.1鍍液組成與特性 13
2.3.3化學鍍銅之反應機制 14
2.4非均溫化學析鍍 17
2.5研究動機 18
3.實驗方法 19
3.1實驗儀器設備 19
3.2實驗藥品 20
3.3實驗操作參數 21
3.3.1化學鍍鎳基合金 21
3.3.1.1鎳磷鍍液組成 21
3.3.1.2鎳鉬磷鍍液組成 21
3.3.1.3基材準備 21
3.3.1.4基材之前處理 21
3.3.1.5操作參數 22
3.3.2化學鍍銅 23
3.3.2.1鍍液之組成 23
3.3.2.2基材前處理 23
3.3.2.3基材準備 23
3.3.2.4基材之前處理 23
3.3.2.5操作參數 23
3.4實驗裝置 25
3.5儀器與方法 26
3.5.1場發射電子顯微鏡(FE-SEM) 26
3.5.2原子力顯微鏡(AFM) 26
3.5.3聚焦離子束與電子束顯微(Forceionbean, FIB) 26
3.5.4X光繞射儀(X-ray Diffractometer) 27
3.5.5電阻率量測 27
3.5.6循環伏安法裝置圖 28
3.6實驗流程 29
4.結果與討論 30
4.1鎳磷合金奈米薄膜製備 30
4.1.1硫酸鎳濃度對微粒粒徑與成膜的影響 30
4.1.2基材加熱溫度對微粒粒徑與成膜的影響 35
4.1.3 pH值對微粒粒徑與成膜的影響 41
4.2鎳鉬磷合金奈米薄膜製備 51
4.2.1鉬酸鈉濃度對微粒粒徑與成膜的影響 51
4.2.2添加不同鉬酸鈉對結構與電性之關係 66
4.2.3對鎳鉬磷合金奈米鍍層上析鍍銅膜結構與電性之關係 70
5.結論 74
參考文獻 75
自傳 79

[1]Y.M. Lin, S.C. Yen, “Effect of additives and chelating agentonel ectroless copper plating,” Applied surface science, Vol. 178, pp.116-126, 2001.
[2]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。
[3]A.A. Istratov, and E.R. Weber, “Electrical properties and recombination activity of copper, nickel and cobalt in silicon,” Applied physics A, Vol. 66, pp 123 1998.
[4]Y.S. Lee, H.S. Woo, J.W. Park, “Effects of heat treatment on electroless copper-deposited film in TaN diffusion barrier,” Materials Science in Semiconductor Processing, Vol. 6, pp. 209-213, 2003.
[5]T. Osaka, N. Takano, T. Kurokawa, T. Kaneko, and K. Uenoc, ”Electroless nickel ternary alloy depositionon SiO2 for application to diffusion barrier layer in copper interconnect technology,” Journal of the electrochemical society, Vol. 149, No. 11 C573-C578, 2002.
[6]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。
[7]A.U. Mane, S.A. Shivashankar, “Atomic layer chemical vapor deposition of copper, ” Materials science in semiconductor processing, Vol.7, pp 343–347, 2004.
[8]H.H. Hsu, C.W. Teng, S.J. Lin, J.W. Yeh, “Sn/Pd Catalyzation and Electroless Cu depositionon TaN diffusion barrier layers,” Journal of the electrochemical society, Vol. 149, No. 9, pp. C143-C149, 2002.
[9]T. Hara, S. Kamijima, Y. 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.
[10]E.J. O’Sullivan, A.G. Schrott, M. Paunovic, C.J. Sambucetti, J.R. Marino, P.J. Bailey, S. Kaja, K.W. Semkow, “Electrolessly deposited diffusion barriers for microelectronics,” IBMJ. res. develop., vol 42, No. 5, pp 607-620, 1998.
[11]M.D. Ger, Y. Sung, J.L. Ou, “A novel process of electroless Ni–P plating by nonisotherma lmethod”, Materials Chemistry and Physics, Vol. 89, pp 383-389, 2005.
[12]Y. Sung, M.D. Ger, Y.H. Chou, “Novel route to deposit metallic dot array or thin film on the conducting and insulating substrates”, Journal of materlals science letters, Vol. 22, pp 1515-1518, 2003.
[13]Y. Sung, M.D.Ger, “The behaviors of a stabilizer in an NITD system with electroless nickel plating“, J. chin. inst. chem. engrs., Vol. 34, No. 5, pp 531-538, 2003.
[14]吳文豪，“鎢錸合金薄膜應用於銅金屬化之擴散阻障層特性研究”，碩士論文，國立交通大學，材料科學與工程研究所，新竹，2003。
[15]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。
[16]鐘鴻欽，“反應性磁控濺鍍鉭及氮化坦基薄膜之微結構及其熱穩定性之研究”，碩士論文，國立成功大學，材料科學及工程學系，台南，2004。
[17]楊聰仁，“無電鍍鈷合金薄膜對銅矽擴散阻障效能之研究”，碩士論文，私立逢甲大學材料科學研究所，台中，2002。
[18]S.D. Yosi, I. Alexandra, S. Yelena, C. Nathan, “Electroless silver and silver with yungsten yhin films for microelectronics and microelectromechanical system applications,” Journal of the electrochemical society, Vol. 147, No. 9, pp 3345-3349, 2000.
[19]C.Y. Lee, T.H. Huang, S.C. Lu, “Diffusion barrier properties of electroless Ni for electroless Cu using Cu plating employing hypophosphite as a reducing agent,” Journal of materlals science: Materlals in electronics, Vol. 9, pp 337-346, 1998.
[20]S. Zhang, J.D. Baets, M. Vereeken, A. Vervat, A.V. Calster, “Stabilizer concentration and localenvirmen : theri effects on electroless nickel plating of PCB micropads,” Journal of the electrochemical society, Vol. 146, No. 8, pp. 2870-2875, 1999.
[21]姜曉霞，沈傳，‘‘化學鍍理論及實踐’’，國防工業出版社，北京，第13-18頁，2000。
[22]W. T. Evans, M. Schelsinger, ‘‘The effect of solution pH and Heat-treatment on the properties of electroless nickel-boron films,’’ Journal of the electrochemical society, Vol. 141, pp. 78-82, 1994.
[23]R.S. Liu, C.C. You, M.S. Tsai, S.F. Hu, Y.H. Li, C.P. Lu, ‘‘An investigation of smooth nano-sized copper plating,’’ Solid state communications, Vol. 125, pp. 445-448, 2003.
[24]V.A. Vas’ko, I. Tabakovic, S.C. Riemer, M.T. Kief, “Effect of organic additiveson structure, resistivity, and room-temperature recrystallization of electrodeposited copper,” Microelectronic engineering, Vol. 75, pp. 71-77, 2004.
[25]宋鈺，“非均溫化學析鍍及其在微結構製備上之應用”，博士論文，國防大學中正理工學院，國防科學研究所，桃園，2003。
[26]程德輝，“化學鍍鎳於非均溫系統之反應機制研究”，碩士論文，國防大學中正理工學院，應用化學研究所，桃園，2002。
[27]范雲智，“非均溫化學鍍銅電化學反應機制之研究”，碩士論文，國防大學中正理工學院，應用化學研究所，桃園，2003。
[28]周育賢，“非均溫化學鍍鎳及同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。
[29]謝美君，“非均溫無電鍍法在基材上製備鎳磷金屬微粒”，碩士論文，國防大學中正理工學院，應用化學研究所，桃園，2004。
[30]鄭吉良，“非均溫化學鍍銅導線製備及其物性分析之研究”， 碩士論文，國防大學中正理工學院，應用化學研究所，桃園，2005。
[31]Y. Wu, C.C. Wan, Y.Y. Wang, “Fabrication of potential NiMoP diffusion barrier/seed layers for Cu interconnects via electroless deposition,” Journal of electronic materlals, Vol. 34, No. 5, pp 541-550, 2005.
[32]渡边側等，于維平，李荻，“非晶态电镀方法及应用”，北京航空航天大學出版社。