目前以銅 取代鋁為連導線 ，因銅連導線有良好的 抗電致遷移率及高導電性，
已經廣泛應用在超大型積體電路 。 但銅容易擴散進入矽晶片。因此，需要在銅連
導線與矽基板中間加上擴散阻障層 以防止銅擴散。 而 元件尺寸日漸小型化導致
溝槽深寬比逐年提高， 傳統濺鍍製 備 Ta/TaN阻障層其沉積覆蓋性較差 ，致使銅
合金自阻障薄膜發展日益重要。 本實驗使用 電化學原子層沉積 製備 Cu(Mn)合金
薄膜， 並研究 Cu(Mn)合金薄膜 之特性 。
本研究在 Ru/Si基板上，利用低電位沉積 製備 出一層錳原子層 接著通入銅
溶液，在開路電位下進行表面侷限氧化還原取代反應將錳置換成銅，利用改變開
路電位時間來獲得不同 Mn含量之 Cu(Mn)合金薄膜， 之後將所得 Cu(Mn)合金薄
膜 經熱處理後探討薄膜 熱穩定 性 。 並以四點探針量測電阻 值 、掃描式電子顯微鏡
觀察表面形貌、能量散布光譜儀進行 薄膜 成分分析、 X-ray繞射儀 進行 結構分析、
感應耦合電漿質 譜分析儀進行成份分析、二次離子質譜儀進行縱深分析。
實驗結果顯示，當鍍液 pH值為 7.5 Mn以 -800 mV UPD沉積 60秒 Cu以 開路電位置換 60秒 為最佳參數設定 初鍍膜具有最低電阻率 20 μΩ-cm
錳含量約 1.72 a.t %。其在快速高溫退火爐 (RTA) 氬氣 +氫氣 (95%+5%)，熱穩
定性可達 600℃。

Use of self-forming Cu alloy thin film is essential for application in state-of-the-art Cu interconnects due to the high aspect ratio of the trenches/vias. The self-forming Cu alloy thin film can be a barrier to prevent Cu diffusion after annealing the film at an elevated temperature by triggering the alloy element diffusion out of the Cu matrix. Thus, the Cu alloy film can potentially replace the conventional Ta/TaN as the barrier and act as the seed layer for Cu electrochemical deposition. However, Cu alloy films were normally deposited by sputter. The sputter deposition can make the film with a low step coverage. In this study, Cu(Mn) alloy thin film was deposited by electrochemical atomic layer deposition, and properties of the Cu(Mn) alloy films were investigated.
The Cu(Mn) films were deposited by alternating underpotential-deposition (UPD) of Mn and surface-limited redox replacement (SLRR) of Cu for 50 cycles. Through these sequences, concentration of the resultant Cu(Mn) film can be adjusted by controlling the replacing time of SLRR-Cu. After that, the Cu(Mn) alloy films were subjected to evaluate the thermal stability. The experimental results show that UPD-Mn deposited at -800 mV for 60 s followed by SLRR-Cu for 60 s can yield a Cu(Mn) film with a resistivity of 20 μΩ-cm. Further, this study shows that the Mn concentration can be successfully controlled by controlling the time of SLRR-Cu. The low-resistivity Cu(Mn) film has a Mn concentration of 1.72 at.%, and is thermally stable up to 600 °C. The proposed method can be a renewed interest in the microelectronics for Cu interconnections.

摘要...................................................i
Abstract...................................................ii
誌謝...................................................iv
目錄...................................................v
表目錄...................................................viii
圖目錄...................................................ix
第一章 緒論...................................................1
1.1 前言...................................................1
1.2 研究動機 ...................................................1
第二章 理論基礎及文獻回顧 ...................................................4
2.1 半導體銅製程...................................................4
2.2 擴散阻障層...................................................4
2.3晶種層與銅錳薄膜之文獻探討..................................................5
2.3.1 釕金屬(Ruthenium, Ru)....................................5
2.3.2 Cu(M)薄膜....................................5
2.3.3 Cu(Mn)薄膜....................................5
2.4 物理氣象沉積(Physcial Vapor Deposition,PVD)...........................6
2.4.1濺鍍系統..................6
2.5 電化學原子層沉積..................7
2.5.1 電化學原子層沉積概念..................7
2.5.2 低電位沉積(Underpotential deposition)..................7
2.5.3 表面侷限氧化還原反應(Surface limited redox replacement).............8
2.6 電化學分析原理..................8
2.6.1 循環伏安法(Cyclic Voltammetry, CV)..................8
2.6.2 計時電流法..................9
2.7 電化學沉核原理..................9
2.7.1電化學反應過程..................9
2.7.2電化學成核理論..................10
2.7.3電化學成核影響因素..................11
2.8 添加劑..................11
第三章 實驗流程與儀器介紹 ..................25
3.1 實驗材料 ..........25
3.1.1 濺鍍靶材 ..........25
3.1.2 實驗基板..........25
3.1.3 製程氣體 ..........25
3.1.4 化學藥品 ..........25
3.2 實驗設備 ..........25
3.3.1 磁控濺鍍系統(Magnetron Sputter System)..........25
3.3.2 pH值校正儀..........26
3.3.3 電化學原子沉積系統(Eilectrochemical Atomic Layer Deposition System, ECALD)..........26
3.3.4 熱處理系統(Annealing System)..........26
3.3 實驗流程..........26
3.2.1 前處理..........27
3.2.2 釕基板製備..........27
3.2.3 電化學原子層沉積系統製備銅錳合金薄膜..........27
3.3.4 溶液配置..........27
3.3.5 熱處理..........27
3.4 分析儀器及原理..........28
3.4.1 四點探針(Four-Point Probbe, FPP)..........28
3.4.2 表面輪廓儀(α-step)..........28
3.4.3 X光繞射分析儀(X-ray Diffraction, XRD)..........28
3.4.4 掃描式電子顯微鏡(Scanning Electron Microscope, SEM)..........28
3.4.5 能量色散X射線光譜儀(Energy Dispersive Spectroscopy,EDS)..........29
3.4.6 感應耦合電漿質譜分析儀（Inductively Coupled Plasma-Mass Spectrometry,ICP-MS）..........29
3.4.7 場發射掃描式電子顯微鏡(Field Emission Gun Scanning Electron Microscopy, FE-SEM)..........29
3.4.8 飛行時間二次離子質譜儀(Time-of-Flight Secondary Ion Mass Spectrometer, TOF-SIMS)..........30
第四章 實驗結果與討論..........43
4.1 沉積電位對錳電化學沉積之特性..........43
4.1.1 循環伏安法探討錳沉積電位..........43
4.1.2 沉積電位對電化學沉積錳薄膜之結構..........43
4.1.3 沉積電位對電化學沉積錳薄膜之表面形貌..........44
4.1.4 沉積電位對電化學沉積錳薄膜成份分析..........44
4.1.5 沉積電位對電化學沉積錳薄膜電性分析..........44
4.2 添加硫酸銨對錳電化學沉積之影響..........44
4.2.1 1mM MnSO4添加1mM (NH4)2SO4溶液之循環伏安圖..........45
4.2.2 沉積電位對電化學沉積錳薄膜之結構..........45
4.2.3 沉積電位對電化學沉積錳薄膜之表面形貌..........45
4.2.4 沉積電位對電化學沉積錳薄膜成份分析..........45
4.2.5 沉積電位對電化學沉積錳薄膜電性分析..........46
4.3 pH值對添加硫酸銨溶液沉積錳薄膜之特性..........46
4.3.1 不同pH值錳溶液之循環伏安圖..........46
4.3.2 沉積電位對電化學沉積錳薄膜之結構..........47
4.3.3 沉積電位對電化學沉積錳薄膜的之表面形貌..........47
4.3.4 沉積電位對電化學沉積錳薄膜電性分析..........47
4.4 以SLRR-Cu置換UPD-Mn沉積Cu(Mn)薄膜特性..........47
4.4.1 以SLRR-Cu置換UPD-Mn開路電位持續不同時間之電壓-電流-時間圖............48
4.4.2 低電位沉積錳薄膜之電流密度-時間變化圖..................49
4.4.3 低電位沉積錳薄膜之成核曲線..................49
4.4.4 開路電位SLRR-Cu置換UPD-Mn之電位-時間變化圖 ..................50
4.4.5 不同開路電位時間截止所得Cu(Mn)薄膜結構..................50
4.4.6 不同開路電位時間截止所得Cu(Mn)薄膜之形貌..................50
4.4.7 不同開路電位截止時間所得Cu(Mn)薄膜之成份..................51
4.4.8 不同開路電位時間所得Cu(Mn)薄膜之電性..................51
4.5 不同開路電位時間所得Cu(Mn)薄膜之熱穩定性探討..................52
4.5.1 Cu(Mn)薄膜不同退火溫度之結構..................52
4.5.2 Cu(Mn)薄膜不同退火溫度薄膜表面分析..................52
4.5.3 Cu(Mn)薄膜不同退火溫度薄膜電性分析..................53
4.5.4 Cu(Mn)薄膜不同退火溫度薄膜SIMS分析..................53
4.6 SLRR-Cu置換UPD-Mn沉積Cu(Mn)薄膜之溝槽填洞能力..................54
第五章 結論..................84
參考文獻..................85
Extended Abstract..................94

[1] M. T. Bohr, International Scaling-The real limiter to high performance ULSI, IEEE, 95 (1995) 241-244.
[2] R.A. Levy, M.L. Green, P.K. Gallager, Characterization of LPCVD Aluminum for VLSI Processing, J. Elcectrochen. Soc., 131(9) (1984) 2175-2182.
[3] C. Whitman, M.M. Moslehi, A. Paranjpe. L. Velo, T. Omstead, Ultralarge scale integrated metallization and interconnects, J. Vac. Sci. Technol. A., 17(4) (1999) 1893-1897.
[4]楊正杰，張鼎張，鄭晃忠，“銅金屬與低介電常數材料與製程”，國家毫米元件實驗室，奈米通訊7卷4期，中華民國89年11月出刊。
[5] 2015, The international technology roadmap for semiconductor, ITRS.
[6] S.T Chen, G.S. Chen, Electroless plating of low-resistivity Cu-Mn alloy thin films with self-forming capacity and enhanced thermal stability, 648 (2015) 474-480.
[7] J.S. Fang, S.L. Sun, Y.L. Cheng, G.S. Chen, T.S. Chin, Cu and Cu(Mn) films deposited layer-by-layer via surface-limited redox replacement and underpotential deposition, Appl. Surf. Sci., 364 (2016) 358-364.
[8]M. Haneda, J. Iijima, J. Koike, Growth behavior of self-formed barrier at Cu–Mn/SiO2 interface at 250–450℃,Appl. Phys. Lett., 90 (2007) 1-3.
[9]T. Usui, H. Nasu, S. Takahashi, N. Shimizu, T. Nishikawa, M. Yoshimaru, H. Shibata, M. Wada, J. Koike, Highly reliable copper dual-damascene interconnects with self-formed MnSixOy barrier Layer, IEEE Trans. Electron Devices, 53 (2006) 2492-2499.
[10]J. Koike, M. Haneda, J. Iijima, M. Wada , “Cu alloy metallization for self-forming barrier process”, In IRPS (Burlingame), (2006) 161–163.
[11]J. Iijima, Y. Fujii, K. Neishi, J. Koike, Resistivity reduction by external oxidation of Cu-Mn alloy films for semiconductor interconnect application, J. Vac. Sci. Technol., 27 (2009) 1963-1968.
[12]S. M. Chung, J. Koike, Analysis of dielectric constant of a self-forming barrier layer with Cu-Mn alloy on TEOS-SiO2, J. Vac. Sci. Technol, 27 (2009) 28-31.
[13] J.R. Lloyd, J.J. Clement, Electromigration in copper conductors, Thin Solid Films, 262 (1995) 135-141.
[14] S. Wolf, Multilevel interconnects for ULSI, in Silicon Processing for the VLSI Era, Deep Submicron Technology, 4 (2002) 573.
[15] Y.S. Diamand, S. Lopatin, Integrated electroless metallization for ULSI, Electrochimi Acta, 44 (1999) 3639-3649.
[16] H.Y. Wong, N.F. Mohd Shukor, N. Amin, Prospective development in diffusion barrier layers for copper metallization in LSI, Microelectron. J., 38 (2007) 777-782.
[17] H. Cai, D. Tong, Y. Wang, X. Song, B. Ding, Reactive synthesis of porous Cu3Si compound, J. Alloys Compd, 509 (2011) 1672-1676.
[18] J.D. McBrayer, R.M. Swanson, Y.W. Sigmon, Diffusion of metals in silicon dioxide, J. Electrochem. Soc., 133 (1986) 1242-1246
[19] M. A. Nicolet, Diffusion Barriers in Thin Films, Thin Solid Films, 52, (1978), 415-443.
[20] R. Chan, T. N. Arunagiri, Y. Zhang, O. Chyan, R. M. Wallace, M. J. Kim, T. Q. Hurd, Diffusion studies of copper on ruthenium thin film, Electrochem. Solid-State Lett., 7 (2004) 154–157.
[21] S.M. Choi,K. C. Park, B. S. Suh, I. R. Kim, H. K. Kang, K. P. Suh, H. S. Park, J. S. Ha, D. K. Joo, Process integration of CVD Cu seed using ALD Ru glue layer for sub-65nm Cu interconnect, IEEE VLSI Tech. Symp.,15-17 (2004) 64-65.
[22] T. N. Arunagiri, Y. Zhang, O. Chyan, M. El-Bouanani, M. J. Kim, K. H. Chen, C. T. Wu, L. C. Chen,5 nm ruthenium thin film as a directly plateable copper diffusion barrier, Appl. Phys. Lett., (2005) 86-88.
[23] D. C. Perng, J. B. Yeh, K. C. Hsu, Ru/WCoCN as a seedless Cu barrier system for advanced Cu metallization,Applied Surface Science, 256 (2009) 688-692.
[24] S.M. Choi, K. C. Park, B. S. Suh, I. R. Kim, H. K. Kang, K. P. Suh, H. S. Park, J. S. Ha, D. K. Joo, Process integration of CVD Cu seed using ALD Ru glue layer for sub-65nm Cu interconnect, IEEE VLSI Tech. Symp., 15-17 (2004) 64-65.
[25] P. C. Andricacos, C. Uzoh, J. O. Dukovic, J. Horkans, and H. Delogianni, “Damascene copper electroplating for chip interconnections”, IBM J. Res. Dev., 42 (1998) 567-574.
[26] F. Cao, Y. Wang, F.Y. Li, B.H. Tang,Evaluation of Cu(Ti) and Cu(Zr) alloys in barrier-less Cu metallization, Materials Chemistry and Physics, 217 (2018) 412-420.
[27] J.H. Park,D.Y. Moon,D.S. Han,Y.J. Kang,S.R. Shin,J.W. Park, ,Self-forming barrier characteristics of Cu–V and Cu–Mn films for Cu interconnects,Thin Solid Films, 547 (2013) 141-145.
[28] J.H. Park, D.-S. Han, K.D. Kim, and J.W. Park, Effects of plasma pretreatment on the process of self-forming Cu–Mn alloy barriers for Cu interconnects, AIP Advances, 8 (2018) 1-7.
[29] K.H. Nagy, F. Misják, In-situ transmission electron microscopy study of thermal stability and carbide formation in amorphous Cu-Mn/C films for interconnect applications, Journal of Physics and Chemistry of Solids, 121 (2018) 312-318.
[30] C. J. Wilson, H. Volders, K. Croes, M. Pantouvaki, G. P. Beyer, A. B. Horsfall, A. G. O’Neill, Z. Tokei, In situ x-ray diffraction study of self-forming barriers from a Cu-Mn alloy in 100 nm Cu/low-k damascene interconnects using synchrotron radiation, Microelectron. Eng., 87 (2010) 398-401.
[31] Y. Otsuka, J. Koike, H. Sako, K. Ishibashi, N. Kawasaki, S. M. Chung, I. Tanaka, Graded composition and valence states in self-forming barrier layers at Cu–Mn/SiO2 interface, Appl. Phys. Lett., 96 (2010) 012101.
[32] J. Gong, G. Wei, J. A. Barnard, G. Zangari, “Electrodeposition and characterization of sacrificial copper–manganese alloy coatings: part II. Structural, mechanical, and corrosion-resistance properties”, Metall. Mater. Trans. 36 (2005) 2705–2715.
[33] F. Mangolini, L. Magagnin, P. l. Cavalloti, “Pulse plating of Mn–Cu alloys on steel”, J. Electrochem. Soc., 153 (2006) 623-628.
[34] J. Koike, M. Wada, Self-forming diffusion barrier layer in Cu–Mn alloy metallization, Appl. Phys. Lett., 87 (2005) 041911.
[35] 張勁燕，2001，“半導體製程設備”，五南圖書出版有限公司，第九章，359。
[36] Sreejith Kaniyankandy , J Nuwad, C Thinaharan, G K Dey, C G S Pillai, Electrodeposition of silver nanodendrites, Nanotechnology, 18 (2007) 125610 1-6 .
[37] S.R. Branlovic, J.X. Wang, R.R. Adzic, Metal monlayer deposition by replacement of metal adlayers on electrode surfaces, Surf. Sci., 474 (2001) 173-179.
[38] S.R Brankovic, J.X. Wang, R.R. ADZIC, New methods of controlled monolayer-to-multilayer deposition of Pt for designing electrocatalysts at an atomic level, J. Serb. Chem. Soc., 66 (2001) 887-898
[39]Quentin Rayée, Thomas Doneux, Claudine Buess-Herman, Underpotential deposition of silver on gold from deep eutectic electrolytes, Electrochimica Acta, 237 (2017) 127-132.
[40] Ej. Calove, and R.A. Etechenique, Kinetic Applications of the Electrochemical Quartz Crystal Microbalance, Comprehensive Chemical Kinetics, R.G. Compton and G. Hancock(Editor), Elservier, Amsterdam,1986.
[41] D. Gokcen, S.E. Bae, S.R. Brankovic, Kinetics of metal deposition via surface-limited redox replacement reaction, ECS Transactions, 35 (2011) 11-22.
[42] J.S. Fang, S.L. Sun, Y.L. Cheng, G.S. Chen, T.S. Chin, Cu and Cu(Mn) films deposited layer-by-layer via surface-limitedredox replacement and underpotential deposition, Appl. Surf. Sci., 364 (2016) 358-364.
[43] V. Venkatasamy, N. Jayaraju, S.M. Cox, C. Thambidurai, M. Mathe, J.L. Stickney, Deposition of HgTe by electrochemical atomic layer epitaxy (EC-ALE), J. Electroanal. Chem., (2006) 195-202.
[44] D. Banga, N. Jarayaju, L. Sheridan, Y.G. Kim, B. Perdue, X. Zhang, Q. Zhang, J. Stickney, Electrodeposition of CuInSe2 (CIS) via electrochemical atomic layer deposition (E-ALD), Langmuir, 28 (2012) 3024-3031.
[45] J.S. Fang, Y.S. Liu, T.S. Chin, Atomic layer deposition of copper and copper silver films using an electrochemical process, Thin Solid Films, 580 (2015) 1-5.
[46] V. Venkatasamy, N. Jayaraju, S.M. Cox, C. Thambidurai, M. Mathe, J.L. Stickney, Deposition of HgTe by electrochemical atomic layer epitaxy (EC-ALE), J. Electroanal. Chem., (2006) 195-202.
[47] J. S. Fang, J. H. Chen, G. S. Chen, Y. L. Cheng, T. S. Chin,Direct, sequential growth of copper film on TaN/Ta barrier substrates by alternation of Pb-UPD and Cu-SLRR, Electrochimica Acta, 206 (2016) 45-51.
[48] K. Venkatraman, R. Gusley, L. Yu, Y. Dordi, R. Akolkar, Electrochemical Atomic Layer Deposition of Copper: A Lead-Free Process Mediated by Surface-Limited Redox Replacement of Underpotentially Deposited Zinc, J. Electrochem. Soc.,163 (2016) D3008-D3013.
[49] D. O. Banga, R. Vaidyanathan, L. Xuehai, J. L. Stickney, S. Cox, U. Happeck, 2008, “Formation of PbTe nanofilms by electrochemical atomic layer deposition (ALD)”, Electrochimica Acta, 53 6988.
[50] T. Oeznuelueer, I. Erdogan, I. Sisman, U. Demir, 2005 , “Electrochemical Atom-by-Atom Growth of PbS by Modified ECALE Method”, Chem. Mater., 17 935.
[51] D. Banga, Y. G. Kim, and J. Stickney, 2011, “PbSe/PbTe Superlattice Formation via E-ALD”, J. Electrochem. Soc., 158, 99.
[52] M. An, J. Zhang, L. Chang, Study of the electrochemical deposition of Sn–Ag–Cu alloy by cyclic voltammetry and chronoamperometry, Electrochimica Acta, 54 (2009) 2883-2889.
[53] Department of Chemical Engineering and Biotechnology, University of Cambridge, Teaching Notes: Electrochemistry Fundamentals, retrieved http://www.ceb.cam.ac.uk/research/groups/rg-eme/teaching-notes
[54] B. Scharifker, G. Hills, Theoretical and experimental studies of multiple nucleation, Electrochimi Acta 28.7 (1983) 879-889.
[55] Peter T. Kissinger, William R. Heineman, Cyclic Voltammetry, Journal of Chemical Education, 60 (1983) 702-706.
[56] Department of Chemical Engineering and Biotechnology, University of Cambridge, Teaching Notes: Electrochemistry Fundamentals, retrieved from http://www.ceb.cam.ac.uk/research/groups/rg-eme/teaching-notes.
[57] A.J. Bard, L.R. Faulkner, Electrochemical Methods Fundamentals and Applications, 2nd, John Wiley and Sons, Inc. (2001).
[58] M. Morisue, Y. Fukunaka, E. Kusaka, R. Ishii, K. Kuribayashi, Effect of gravitational strength on nucleation phenomena of electrodeposited copper onto a TiN substrate, J. Electroanal. Chem., 559 (2003) 155-163.
[59]D. Turnbull, J.C. Fisher, Rate of nucleation in condensed systems, The J. Chem. Phys., 17 (1949) 71-73.
[60] A. Bewick, M. Fleischmann, H. R. Thirsk, Kinetics of the electrocrystallization of thin films of calomel, Transactions of the Faraday Society, 58 (1962) 2200-2216.
[61] B. Scharifker, G. Hills, Theoretical and experimental studies of multiple nucleation, Electrochimi Acta, 28 (1983) 879-889.
[62] B.J. Hwang, R. Santhanam, Y.L. Lin, Nucleation and growth mechanism of electroformation of polypyrrole on a heat-treated gold/highly oriented pyrolytic graphite, Electrochim. Acta, 46 (2001) 2843-2853.
[63] T.P. Moffat, D. Wheeler, D. Josel, Electrodeposition of copper in the SPS-PEG-Cl additive system I. Kinetic measurements: Influence of SPS, J. Electrochem. Soc., 151 (2004) C262-C271.
[64] B. J. Hinch, C. Koziol, J.P. Toennies, G. Zhang, Single and double layer growth mechanisms induced by quantum size effects in Pb films deposited on Cu (111), Vac., 42 (1991) 309-311.
[65] B. Rashkova, B. Guel, R.T. PoÈ tzschke, G. Staikov, W.J. Lorenz, Electrodeposition of Pb on n-Si(111), Electrochimi. Acta, 43 (1998) 3021-3028.
[66] P.C.T.D. Ajello, M.L. Munford, A.A. Pasa, Transient equations for multiple nucleation on solid electrodes: a stochastic description, J. chem. Phys., 111 (1999) 4267-4272.
[67] I. Danaee, 2D-3D nucleation and growth of palladium on graphite electrode, Ind. Eng. Chem., 19 (2013) 1008-1013.
[68] K. Raeissi, A. Saatchi, M.A. Golozar, Effect of nucleation mode on the morphology and texture of electrodeposited zinc, J. Appl. Electrochem., 33 (2003) 635-642.
[69] J.L. Delplancke, M. Sun, T.J. OKeefe, R. Winand, Nucleation of electrodeposited copper on anodized titanium, Hydrometallurgy, 23 (1989) 47-66.
[70] G.Gunawardena, G.Hills, I. Montenegro, B. Scharifker, Electrochemical nucleation: Part I. general considerations, J. Electroanal. Chem., 138 (1982) 225-239.
[71] D. Grujicic, B. Pesic, Reaction and nucleation mechanisms of copper electrodeposition from ammoniacal solutions on vitreous carbon, Electrochimi Acta, 50 (2005) 4426-4443.
[72]D. Grujicic, B. Pesic, Electrodeposition of copper: the nucleation mechanisms, Electrochimi Acta, 47 (2002) 2901-2912.
[73] O. Renault, A Garnier, J Morin, N Gambacorti, High-resolution XPS spectromicroscopy study of micro-patterned gold–tin surfaces, Appl. Surf. Sci., 258 (2012) 10077-10083.
[74] L. Oniciu, L. Muresan, Some fundamental aspects of leveling and brightening in metal electordepostion, J. Appl. Electrochem., 21 (1991) 565-574.
[75] H. Natter, R. Hempelmann, Nanocrystalline Copper by Pulsed Electrodeposition: The Effects of Organic Additives, Bath Temperature, and pH, J. Phys. Chem., 100 (1996) 19525-19532.
[76] Y. M. Lin, S.C. Yen, Effects of additives and chelating agents on electroless copper plating. Appl. surf. Sci., 178 (2001) 116-126.
[77] W.Z. Xu, J.B. Xu, H.S. Lu, J.X. Wang, Z.J. Hu, X.P. Qu, Direct copper plating on Ultra-Thin sputtered cobalt film in an alkaline bath, J. Electrochem. Soc., 160 (2013) D3075-D3080.
[78] P. Wei, O. Hileman, M.-R. Bateni, X. Deng, A. Petric, Manganese deposition without additives, Surf. Coat. Technol. 201 (2007) 7739–7745.
[79] P. Díaz-Arista, R. Antaño-López, Y. Meas, R. Ortega, E. Chainet, P. Ozil, G. Trejo, EQCM study of the electrodeposition of manganese in the presence of ammonium thyociante in chloride-based acidic solutions, Electrochim. Acta 51 (2006) 4393–4404.
[80] J. Lewis, P. Scaife, D. Swinkels, Electrolytic manganese metal from chloride electrolytes. I. Study of deposition conditions, J. Appl. Electrochem. (1976) 199–209.
[81] J. Lewis, P. Scaife, D. Swinkels, Electrolytic manganese metal from chloride electrolytes. II. Effect of additives, J. Appl. Electrochem. 6 (1976) 453–462.
[82]J.H. Jacobs, J.W. Hunter, W.H. Yaroll, P.E.Churchward, R.G. Knikerbocker,Operations of Electrolytic Manganese Pilot Plant at Boulder City, Nevada, Technical Report 463United States Department of Interior—Bureau of Mines, Boulder City, USA (1946)
[83] J. Lu, D. Dreisinger, T. Gluck, Manganese electrodeposition-Aliterature review,141 (2014) 105-116.
[84] X. Zhang,Z. Liu,C. Tao,X. Quan,Pulse current electrodeposition of manganese metal from sulfate solution,Journal of Environmental Chemical Engineering, 7 (2019) 103010.
[85] M. Hareifar, M. Zandrahimi, Effect of current density and electrolyte pH on microstructure of Mn–Cu electroplated coatings, Applied Surface Science, 284 (2013) 126-132.
[86] M. F. Barcia , V. Hoffmann, S. Oswald, L. Giebeler, U. Wolff, M. Uhlemann, A. Gebert , Electrodeposition of manganese layers from sustainable sulfate based electrolytes, Surface and Coatings Technology, 334 (2018) 261-268.
[87]G. Zangari, J. Gong, Electrodeposition and characterization of manganese coatings, J. Electrochem. Soc., 149 (2002) C209-C217.
[88] L. Yu, Z. Vashaei, F. Ernst, R. Akolk, Electroless Deposition of Copper-Manganese for Applications in Semiconductor Interconnect Metallization, J. Electrochem. Soc., 163 (2016) D374-D378.
[89]T. Muppidi, D.P. Field, J.E. Sanchez Jr, C. Woo, Barrier layer,geometry and alloying effects on the microstructure and texture of electroplated copper thin films and damascene lines, Thin Solid Films, 471 (2005) 63-70.
[90] J. Koo, S.K. won, N.R. Kim, K. Shin, H.M. Lee, Ethylenediamine-enhanced oxidation Resistivity of a Copper Surface during Water-Based Copper Nanowire Synthesis, J. Phys. Chem. 120 (2016) 3334-3340.
[91] Christopher J. Wilson Henny Volders KristofCroes,Marianna Pantouvaki,Gerald P. Beyer.Alton B.Horsfall,Anthony G.O’Neill,Zsolt Tőkei,In situ X-ray diffraction study of self-forming barriers from a Cu–Mn alloy in 100 nm Cu/low-k damascene interconnects using synchrotron radiation,Microelectronic Engineering,87 (2010) 398-401.
[92]Zs.Czigány, F.Misják, O.Geszti, G.Radnóczi, Structure and phase formation in Cu–Mn alloy thin films deposited at room temperature,Acta Materialia,60 (2012) 7226-7231.
[93] H.J. Lee,T. E. Hong,S.H. Kim,Atomic layer deposited self-forming Ru-Mn diffusion barrier for seedless Cu interconnects,Journal of Alloys and Compounds,686 (2016) 1025-1031.
[94] http://resource.npl.co.uk/mtdata/phdiagrams/cumn.htm
[95]C.Y. Wu, C.T. Wu,W.H. Lee, S.C. Chang,Y.L. Wang,A study on annealing mechanisms with different manganese contents in CuMn alloy,Journal of Alloys and Compounds, 542 (2012) 118-123.