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姓名	段生振(Sheng-Chen Twan)  查詢紙本館藏	畢業系所	材料科學與工程研究所
論文名稱	離子佈植對鎳合金矽化物之生成行為研究 (Formation Behaviors and Microstructures of Nickel Alloy Silicide with Ion Implantation)
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摘要(中)	矽集體電路的尺寸微縮，一直追隨摩爾定律向高階製程挑戰，也因此降低互補式金屬氧化物半導體場效電晶體的接觸電阻，為矽集體電路半導體製造中最重要的課題之一。離子佈植係將各種不同的元素植入不同基材中，以改變材料特性及晶格之結構，進而降低電晶體的接觸電阻，於半導體製造程序具有重要之地位，這也是最近這幾十年來被廣泛應用於半導體製造的重要生產技術之一。 本論文系統性地針對離子佈植或其他沉積技術將元素添加於鎳合金矽化物後，其生成之行為作一深入的探討與研究，以期解決對互補式金屬氧化物半導體場效電晶體微縮的挑戰，進而提昇半導體元件的性能。 首先，經由實驗發現添加鋁於矽基材 (001) 之鎳矽化物中，其鎳合金矽化物之熱穩定性會相對提高；同時，也因為鋁原子的添加，而延緩矽化二鎳–矽化鎳化合物相變化的速度，更進一步加速了二矽化鎳鋁化合物於退火時相變化之速率。鎳合金矽化物的相變化速率，初期主要是受鋁原子於鎳鋁合金中的濃度影響，在比較Ni0.95Pt0.05/Si 和Ni0.95Al0.05/Si system 系統後，發現Ni0.91Al0.09/Si合金展現了很高的熱穩定性，縱使處於高溫退火1000秒之後，依然能保持良好的熱穩定性。本實驗也同時針對鋁原子對鎳矽化物的微結構、電性和熱穩定性的關係做進一步的探討與研究。經由本實驗證實，鎳鋁矽化合物因具有高溫熱穩定性的優點，可有效應用於先進互補式金屬氧化物半導體場效電晶體元件之源極/汲極接觸製程材料，以提升元件的性能。 另一實驗係針對鈦離子於不同矽基材中對所形成的鎳矽化物之影響，並藉由TEM, GIXRD, XPS, and Raman等分析以進一步深入的探討與研究。結果顯示，鎳鈦矽化合物實驗系統中，由於鈦原子的低熔解率和低擴散速率，只有二矽化鎳化合物的產生。而且，在預離子佈植非晶質之矽基材上，由於離子佈植氙原子產生之非晶質矽，會抑制二矽化鎳化合物的生長，降低了鈦原子的自由能，在驅動力不足的情況下，而驅使鈦原子向非晶矽與結晶矽的介面堆積，又在高溫環境下形成二氧化鈦，阻止了鎳原子向矽基材擴散。因此，於預離子佈植非晶質之矽基材上的鎳矽化合物，若植入或沉積鈦離子後所生成的鎳鈦矽化合物，不僅會提昇鎳矽化合物生成的溫度，也會提高材料的熱穩定性，進而降低蕭特基能障，並降低接觸片電阻，進而提昇半導體元件之性能。
摘要(英)	With the scaling of IC devices on Moore’s Law extension, the contact sheet resistance reduction is crucial on IC device fabrication. Ion implantation with additives elements for material modification and structural crystallization is one of the most critical methods for contact resistance reduction. It is also being widely used at semiconductor manufacturing in recent decades. This dissertation systematically investigated the formation behaviors and microstructures of Nickel silicide with ion implantation or deposited the additive elements for contact sheet resistance reduction to addressed the CMOS transistors scaling challenges as well as device performance improvement. Firstly, the experimental results showed the thermal stability of Nickel silicide was improved by adding Aluminum (Al) into Nickel silicides on Silicon (Si) (001), and the phase transformation of Ni2Si to NiSi was also retarded by adding Al atoms, it was also significantly speeds up the NiSi2-xAlx formation during annealing. The behavior of Nickel silicide phase transformation is strongly depending on the Al concentration of the initial Ni1-xAlx alloys. Compared to the Ni0.95Pt0.05/Si and Ni0.95Al0.05/Si system, the Ni0.91Al0.09/Si sample exhibits remarkably enhanced thermal stability, even after high temperature annealing for 1000 second. The relationship between microstructures, electrical property, and thermal stability of Ni silicide is discussed to elucidate the role of Al during the Ni1-xAlx alloy silicidation. This work demonstrated the Ni1-xAlx alloy silicide thermal stability would be a promising candidate as source/drain (S/D) contacts material in advanced complementary metal–oxide semiconductor (CMOS) devices. Secondly, the experiment is systematically investigated the effects of Ti-doped Nikel silicide on different substrates during the Nickel silicidation, especially on the Pre-amorphous Ion Implantation Si substrate with Xenon (Xe) ion implantation. The TEM, GIXRD, XPS, and Raman were used for metrology analysis. Due to lower diffusion rate and lower solubility of Titanium atoms in Ni0.9Ti0.1 on both Si and pre-amorphous ion implant Si (PAI-Si) substrates, it led to the NiSi2 formation. The formation of NiSi2, will reduce the free energy and force the Titanium atoms accumulated at the interface, then transformed into TiO2 at higher temperature to prevent the Nickle diffuses into the substrates. Especially on PAI-Si, the implanted Xe atoms will postpones the formation of NiSi2 and reduce the free energy, force the Titanium accumulated at the crystalline/ amorphous interface as diffusion barrier layer. Thus, in PAI Si substrate, the Titanium Nickel silicide will increase the formation temperature of NiSi2, which could increase the thermal stability, but also reduce the Schottky Barrier Height for contact resistance reduction to boost the CMOS devices performance.
關鍵字(中)	★ 鎳矽化合物 ★ 接觸片電阻 ★ 熱穩定性 ★ 離子佈植	關鍵字(英)	★ Nickel silicide ★ Contact Sheet resistance ★ Thermal stability ★ Ion Implantation
論文目次	Contents 摘要 ..................................................... I Abstract ............................................... III 誌謝 ..................................................... V Contents ................................................ VI List of Figures.......................................... XI List of Tables ....................................... XVIII Chapter 1 Introduction ................................... 1 1.1 Introduction of Silicon Integrated Circuits ................................................. 1 1.2 The Operational Principles of MOSFET Transistors .............................................. 5 1.3 CMOS Technology Roadmap .................................................. 7 1.4 The Challenges of Silicon CMOS Scaling .................................................. 9 1.5 Gate Leakage Improvement ............................ 11 1.5.1 De-coupled Plasma Nitridation (DPN) ................................................... 11 1.5.2 Atomic Layer Deposition (ALD) ................... 12 1.5.3 Physical Vapor Deposition (PVD) ................. 12 1.6 Mobility Enhancement ................................ 12 1.6.1 Selective Epitaxial Growth ...................... 12 1.6.2 Strained Silicon Nitride ........................ 13 1.6.3 Stress Memorization Technique (SMT) ............... 13 1.6.4 Replacement with Metal Gate ....................... 14 1.7 Parasitic Resistance ................................ 14 1.7.1 Ion Implantation ................................ 15 1.7.2 Atomic Layer Deposition ......................... 15 1.7.3 Pre-silicide Amorphization ...................... 15 1.7.4 Parasitic Capacitance ........................... 15 1.8 From 2D Planar to 3D FinFET CMOSFET ................. 16 1.9 The Challenges of FinFET Devices .................... 17 1.9.1 The effective gate length (Leff) reduction ...... 17 1.9.2 The gate pitch dimension reduction .............. 18 1.9.3 Threshold Voltage (Vt) Control .................. 18 1.10 Formation of High K/Metal Gate ..................... 20 1.10.1 High K Dielectric .............................. 20 1.10.2 Metal Gate ..................................... 20 1.11 Summary ............................................ 22 1.12 Figures ............................................ 23 1.13 Tables ............................................. 50 Chapter 2 Analysis of Contact Resistance Reduction ...... 54 2.1 Introduction of Parasitic Resistance Wafer preparation ............................................. 54 2.2 Introduction of Silicides ........................... 58 2.3 The Key Challenges of Nickel Silicides .............. 59 2.4 Latest Approaches to address Nikel Silicides Challenges .............................................. 60 2.4.1 Added Platinum (Pt) ............................. 60 2.4.2 PAI (Pre-Amorphous Implant) Si .................. 61 2.4.3 Combined Implant and anneal process ............. 62 2.4.4 Some other processes with implantation .......... 62 2.5 Figures ............................................. 64 2.6 Tables .............................................. 71 Chapter 3 Influence of Al addition on phase transformation and thermal stability of Nickel silicides on Si (001) ... 73 3.1 Introduction ........................................ 73 3.2 Experimental Tools and Metrology .................... 74 3.2.1 Four Point Probes ............................... 74 3.2.2 Scanning Electron Microscope (SEM) .............. 75 3.2.3 Energy Dispersive Spectrometer (EDS) Analysis ... 75 3.2.4 Preparation of Samples for Transmission Electron Microscope (TEM) Observation ............................ 75 3.2.5 Transmission Electron Microscope Observation .... 76 3.2.6 X-ray Diffraction (XRD) Analysis ................ 76 3.2.7 Sputtering ...................................... 76 3.3 Experimental Details ................................ 77 3.4 Results and Discussion .............................. 78 3.5 Conclusions ......................................... 82 3.6 Figures ............................................. 84 Chapter 4 Ni(Ti) silicide formation on pre-amorphous implanted Si (001) ...................................... 90 4.1 Introduction ........................................ 90 4.2 Experimental Tools and Metrology .................... 91 4.2.1 Grazing Incidence X-Ray Diffractometry (GIXRD) .. 91 4.2.2 Ion Implantation ................................ 92 4.3 Experimental Details ................................ 92 4.4 Results and Discussion .............................. 94 4.5 Conclusions ......................................... 97 4.6 Figures ............................................. 99 Chapter 5 Future Works ................................. 107 5.1 Ultrathin Ni1-xPtx Silicide in CMOS Device ......... 107 5.2 SBH Reduction with Ion Implantation ................ 108 5.3 Figures ............................................ 109 References ............................................. 112
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Wong et al., “F-enhanced morphological and thermal stability of NiSi films on BF2+-implanted Si(001)”, Applied Physics Letter, vol.81, pp.5138-5140, 2002. [2.34] P.S. Lee et al., “Improved NiSi salicide process using presilicide N2+ implant for MOSFETs”, IEEE Electron Device Letter, vol.21, pp.566-568, 2000. [2.35] B.Y. Tsui et al., “Improvement of the thermal stability of NiSi by germanium ion implantation”, Journal of Electrochemistry Society, vol.157, pp.137-143, 2010. [2.36] O. Nakatsuka et al., “Improvement in NiSi/Si contact properties with C-implantation”, Microelectronic Engineering, vol.82, pp.479-484, 2005. [2.37] N. Variam et al., “The contact engineering with ion implantation”, Technology Symposium, 2013. Chapter 3 Influence of Al addition on phase transformation and thermal stability of nickel silicides on Si (001) [3.1] A. Lauwers et al., “Ni based silicides for 45 nm CMOS and beyond, Material Science Engineering, vol.B, pp.114–115, 2004. [3.2] M. Sinha et al., “Novel aluminum segregation at NiSi/p+-Si source/drain contact for drive current enhancement in p-channel FinFETs”, IEEE Electron Devices Letter, vol.30, pp.85-87, 2009. [3.3] Z. Zhang et al., “Exploitation of a self-limiting process for reproducible formation of ultrathin Ni1−xPtx silicide films”, Applied Physics Letter, vol.97, 252108, 2010. [3.4] C.J. Choi et al., “Thickness effect of a Ge interlayer on the formation of nickel silicides” Journal of Electrochem. Society, vol.154, pp.759-763, 2007. [3.5] S.W. Lee et al., “C redistribution during Ni silicide formation on Si1-yCy epitaxial layers”, Journal of Electrochem. Society, vol.157, pp.297-300, 2010. [3.6] C. Boulord et al., “Electrical and structural characterization of electroless nickel–phosphorus contacts for silicon solar cell metallization”, J Journal of Electrochem. Society. vol.157, pp.742-745, 2010. [3.7] K.D. Keyser et al., “Phase formation and thermal stability of ultrathin nickel-silicides on Si(100)”, Appl. Phys. Lett., vol.96, 173503, 2010. [3.8] K.R. Lee et al., “Thermal stability of Ni(Ta) silicide films on ultra-thin silicon-on-insulator substrates”, Journal of Alloys and Compounds, in press, 2010. [3.9] K. Hoummada et al., “Effect of Pt addition on Ni silicide formation at low temperature: Growth, redistribution, and solubility, Journal of Applied Physics, vol.106, 063511, 2003. [3.10] D. Deduytsche, et al. “Influence of Pt addition on the texture of NiSi on Si(001)”, Appl. Phys. Lett., vol.84, pp.3549-3551, 2004. [3.11] J. Demeulemeester et al., “Pt redistribution during Ni(Pt) silicide formation”, Appl. Phys. Lett., vol.93, 261912, 2008. [3.12] D. Mangelinck et al., “Enhancement of thermal stability of NiSi films on (100)Si and (111)Si by Pt addition”, Appl. Phys. Lett., vol.75, pp.1736-1738, 1999. [3.13] D. Deduytsche et al., “Formation and morphological stability of NiSi in the presence of W, Ti, and Ta alloying elements”, Journal of Applied Physics, vol.101, 044508, 2007. [3.14] S.L. Chiu et.al., “ Effects of Ti interlayer on Ni/Si reaction systems”, J. Electrochem. Soc., vol.157, G452-G455, 2004. [3.15] P. Gergaud et al., “Stresses arising from a solid state reaction between palladium films and Si(001) investigated by in situ combined x-ray diffraction and curvature measurements”, J. Appl. Phys., vol.94, pp.1584-1591, 2003. [3.16] M. Chan et al., “Recessed-channel structure for fabricating ultrathin SOI MOSFET with low series resistance”, IEEE Trans. Electron Devices, vol.15, pp.22-24, 1994. [3.17] E. Alptekin et al., “Schottky barrier height of nickel silicide contacts formed on Si1−xCx epitaxial layers”, IEEE Electron Devices Lett., vol.30, pp. 1320-1322, 2009. [3.18] J.M. Larson et al., “Overview and status of metal S/D Schottky-barrier MOSFET Technology”, IEEE Electron Device Lett., vol.53, pp.1048-1058, 2006. [3.19] W.J. Lee et al., “Work function variation of nickel silicide using an ytterbium buffer layer for Schottky barrier metal-oxide-semiconductor field-effect transistors”, J. Appl. Phys., vol.101, 103710, 2007. [3.20] M. Sinha et al., “Tuning the Schottky barrier height of nickel silicide on p-silicon by aluminum segregation, Appl. Phys. Lett., vol.92, 222114, 2008. [3.21] R.T.P. Lee et al., “Achieving conduction band-edge Schottky barrier height for arsenic-segregated nickel aluminide disilicide and implementation in FinFETs with ultra-narrow Fin widths”, IEEE Electron Device Letter, vol.29, pp.382-385, 2008. [3.22] A.T.Y. Koh et al., “Nickel-aluminum alloy silicides with high aluminum content for contact resistance reduction and integration in n-Channel field-effect transistors”, J. Electrochem. Soc., vol.155, H151-H155, 2008. [3.23] S.W. Lee et al., “Ni silicide formation on epitaxial Si1−yCy/(001) layers, Thin Solid Films, vol.518, pp.7394-7397, 2010. [3.24] L.J. Chen et al., “In situ TEM investigation of dynamical changes of nanostructures”, Mater. Sci. Eng., vol.70, pp.303-319, 2010. [3.25] K.W. Richter et al., “NiAi1.74Si0.26 and NiSi1.83Ga0.17: Two materials with perfect lattice match to Si”, Applied Physics Lett., vol.83, pp. 497-499, 2003. [3.26] R.T.P. Lee et al., “Novel nickel-alloy silicides for source/drain contact resistance reduction in n-channel multiple-gate transistors with sub-35nm gate length, Tech. Dig. - Int. Electron Devices Meeting, pp.851-854. [3.27] A. Mogilatenko et al., Journal of Applied Physics, vol.111, pp.103~105, 2012. [3.28] K. Tsutsui et al., Microelectron. Engineering, vol.85, pp.2000–2004, 2008. [3.29] F. Allenstein et al., Microelectron. Eng., vol.82, pp.474–478, 2005. Chapter 4 Ni(Ti) silicide formation on pre-amorphous implanted Si (001) [4.1] R.W. 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Qu et al., “Thermal stability, phase and interface uniformity of Ni-silicide formed by Ni-Si solid-state reaction”, Thin Solid Films., vol.462, pp.146-150, 2004. [4.11] J. Demeulemeester et al., “Pt redistribution during Ni(Pt) silicide formation”, Appl. Phys. Lett., vol.93, 261912, 2008. [4.12] D. Lee et al., “The effects of Ta on the formation of Ni-silicide in Ni0.95xTax0.05/Si systems”, Mater. Sci. Eng., B. 114, pp.241-245, 2004. [4.13] Y. Setiawan et al., “Effect of Ti alloying in nickel silicide formation”, Thin Solid Films., vol.504, pp.153-156, 2006. [4.14] F. Allenstein et al., “Influence of Al on the growth of NiSi2 on Si(001)”, Microelectronic Engineering, vol.82, pp.474-478, 2005. [4.15] K. Tsutsui et al., “Improvement of thermal stability of Ni silicide on N+-Si by direct deposition of group III element (Al, B) thin film at Ni/Si interface”, Microelectronic Engineering, vol.85, pp.2000-2004, 2008. [4.16] J. Luo, Y.L. Jiang, G.P. Ru, B.Z. Li, P.K. Chu, Silicidation of Ni(Yb) film on Si(001), J. Electron. Mater., vol.37, pp.245-248, 2008. [4.17] W. Huang et al., “The improvement of thermal stability of nickel silicide by adding a thin Zr interlayer”, Microelectron. Engineering, vol.83, pp.345-350, 2006. [4.18] W. Huang et al., “Effect of a thin W, Pt, Mo, and Zr interlayer on the thermal stability and electrical characteristics of NiSi”, Microelectron. Eng., vol.84, pp.678-683, 2007. [4.19] W. Huang et al., “Effect of erbium interlayer on nickel silicide formation on Si(100)”, Appl. Surf. Sci., vol.254, pp.2120-2123, 2008. [4.20] A.S.W. Wong et al., “F-enhanced morphological and thermal stability of NiSi films on BF2+-implanted Si(001)”, Applied Physics Letter, vol.81, pp.5138-5140, 2002. [4.21] P.S. Lee et al., “Improved NiSi salicide process using presilicide N2+ implant for MOSFETs”, IEEE Electron Device Letter, vol.21, pp.566-568, 2000. [4.22] B.Y. Tsui et al., “Improvement of the thermal stability of NiSi by germanium ion implantation”, Journal of Electrochemistry Society, vol.157, pp.137-143, 2010. [4.23] O. Nakatsuka et al., “Improvement in NiSi/Si contact properties with C-implantation”, Microelectronic Engineering, vol.82, pp.479-484, 2005. [4.24] Z. Kuwano et al., Appl. Phys. Lett., vol.56, pp.440-442, 1990. [4.25] R.W. Hoffman et al., Physics of Thin Films, Vol. 3, Academic Press, New York, pp.211, 1996. [4.26] D. Mangelinck et al., Appl. Phys. Lett., vol.75, pp.1736-1738, 1999. [4.27] L.J. Chen et al., Mater. Sci. Semicond. Process., vol.4, pp.237-240, 2001. [4.28] C.J. Tsai et al., Thin Solid Film, vol.365, pp.72-76, 2000. [4.29] C.J. Tsai et al., Thin Solid Film, vol.350, pp91-95, 1999. [4.30] S.W. Lu et al., Appl. Phys. Lett., vol.49, pp.1770-1772, 1986. [4.31] Y.N. Erokhin at al., Appl. Phys. Lett., vol.63, pp3173, 1993. [4.32] U. Falke et al., Phys. Stat. Sol., vol. (a). 162, pp.615-621, 1997. [4.33] C.D. Line, et al., “Low temperature formation of NiSi2 from evaporated Silicon”, Phys. Stat. Sol., (a). vol.81, pp.123-128, 1984. [4.34] J. Lu et al., Electrochem. Solid-State Lett., vol.13, pp.360-362, 2010. Chapter 5 Future Works [5.1] Shi-Li Zhang, “Untrathin Ni1-xPtx films as electrical contact in CMOS devices, ECS Trans”, vol. 45, Issue 6, pp.15-22, 2012. [5.2] K. De Keyser et al., “Phase formation and thermal strability of untrathin Nickel Silicide on Si”, Applied Physics, Letter 96. 173503, 2010. [5.3] Y. Nishi et. al, “Silicide wok function tuning by alloy approaches", IEEE International Electrical Device Meeting, pp. 135, 2007. [5.4] Z. Zhang et. al, “Interface Dipole Engineering by dopant segregation”, IEEE International Electrical Device Meeting, vol. 28, No.7, pp.565, 2007.
指導教授	李勝偉(Sheng-Wei Lee)	審核日期	2017-10-11
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