金屬矽化物因具有高熔點、良好熱穩定性、及低電阻等優點，故其在VLSI半導體製程上有相當廣泛的應用。隨著傳統微影術(lithography)在最小線寬上所面臨的瓶頸，一種「由下而上」(bottom up)的「自我組裝」(self-assembly)合成方式開始引起廣泛研究與討論。
本論文以合成自我組裝磊晶金屬矽化物奈米線為主體，研究其生長機制，並進一步藉由製程上對於其成長動力學的控制來加以控制奈米線的形貌，增加其長寬比(aspect ratio)，包括使用「反應性蒸鍍磊晶」(reactive deposition epitaxy)與「氮化矽非晶層調節磊晶」(nitride-mediated epitaxy)等方法。主要的研究是在鐵、鈷、鎳等過渡金屬(transition Metal)矽化物上。並利用電子顯微鏡等儀器進行觀察與分析。
研究上首先是利用反應性蒸鍍磊晶法成長矽化鎳奈米線,基於「形狀轉變」(shape transition)理論,金屬原子蒸鍍在加熱的矽基板上將有足夠的動能使其在矽基表面移動，貼附於已生成的矽化物晶粒之上並以一維成長的方式來降低總能量。加熱的溫度對所生成的矽化物奈米線形貌影響很大，在750 ℃下我們可得到磊晶成長於矽基上，長寬比達30的自我組裝矽化鎳奈米線
以此方式生長的奈米線，在成長過程中牽涉到原子的再排列(rearrangement)，奈米線的生長與否將取決於原子再排列的速度與矽化物成長的速度，在前者佔優勢的情況下，奈米線方得以生成。因此我們首先利用在矽基上先鍍上一層非晶質氮化矽薄膜的方式，來降低蒸鍍原子到達矽基上的通量，進而降低矽化物體積的成長速率，而達成促進矽化物奈米線生長之目的，我們成功的將此方法運用於鐵、鈷、鎳等過鍍金屬矽化物系統之上，生長出高長寬比的矽化物奈米線。在鎳化矽系統上，利用此方式將可使得奈米線的長寬比提升達八倍。而在矽化鐵系統上，極慢的生長速率使得我們能藉由加熱時間來控制奈米線的長度。
另一種方法則是在蒸鍍源中掺入金原子，金在矽化物生長時會在矽化物與矽基的界面偏析，由於金跟矽的共晶溫度非常低(360 ℃)，因此在成長溫度下矽化物與矽的界面會形成一局部熔融的通道，原子再排列的過程能藉由此通道而快速進行，因而達到促進矽化物奈米線之目的。

Self-assembled epitaxial NiSi2 nanowires have been fabricated on (001)Si by reactive deposition epitaxy (RDE). The RDE method promoted nanowire growth since it provides deposited atoms sufficient kinetic energy for movement on the Si surface during the growth of silicide islands. The twin-related interface between NiSi2 and Si is directly related to the nanowire formation since it breaks the symmetry of the surface and leads to the asymmetric growth. The temperature of RDE was found to greatly influence the formation of nanowires. By RDE at 750 °C, a high density of NiSi2 nanowires was formed with an average aspect ratio of 30.
Self-assembled NiSi2 nanowires with a high-aspect ratio have been fabricated by combining the methods of RDE and nitride-mediated epitaxy (NME). Both types of epitaxial NiSi2 nanowires, which are parallel and twin related to the substrates, were formed with the length/width aspect ratios increased by a factor of 8 with the effect of NME. One type of nanowire was successfully grown with a high-aspect ratio despite the four-fold symmetric epitaxial relationship between NiSi2 and Si with very small mismatch. The use of NME method effectively diminished the flux of Ni atoms and allowed sufficient time for the strain to be released by means of shape transition during the island growth at elevated temperatures.
Endotaxial growth of self-assembled α-FeSi2 nanowires on (100)Si has been achieved by combining RDE and NME. The length and the length/width aspect ratio of metallic α-FeSi2 nanowires could be increased more than 12 and 6 folds to 2 μm, and 200 respectively, with a narrow width of 5-10 nm after prolonged annealing. The adjustment capability is attributed to the diminished flux of Fe adatoms mediated by the Si3N4 barrier layer to allow more complete shape transition. The scheme represents a degree of control on the morphology of self-assembled epitaxial silicide NWs not achievable otherwise.
Au-Ni alloy have been used as metal source of RDE to enhance the growth of self-assembled silicide nanowires. The rate of adatom rearrangement can be increased significantly by the formation of a fast diffusing path at the silicide/Si interface as a result of the low Au-Si eutectic point. The result demonstrated an essential role of the rearrangement of atoms in the process of formation of epitaxial silicide NWs.

Chapter 1
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Chapter 2
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Chapter 3
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3.2 Y. Huang, X. Duan, Q. Wei, and C. M. Lieber, “Directed Assembly of One-Dimensional Nanostructures into Functional Networks,” Science 291, 630-633 (2001).
3.3 M. S. Fuhrer, J. Nygard, L. Shih, M. Forero, Y. Yoon, M. S. C. Mazzoni, H . J. Choi, J. Ihm, S. G. Louie, A. Zettl, and P. L. McEuen, “Crossed Nanotube Junctions,” Science 288, 494-497 (2000).
3.4 M. T. Bjork, B. J. Ohlsson, C. Thelander, A. I. Persson, K. Deppert, L. R. Wallenberg, and L. Samuelson, “Nanowire Resonant Tunneling Diodes,” Appl. Phys. Lett. 81, 4458-4460 (2002).
3.5 L. J. Chen, “Metal silicides: An Integral Part of Microelectronics,” JOM 57 (9), 24-30 (2005).
3.6 Y. Wu, J. Xiang, C. Yang, W. Lu, and C.M. Lieber, “Single-Crystal Metallic Nanowires and Metal/Semiconductors Nanowires Heterostructures,” Nature 430, 61-65 (2004).
3.7 J. F. Lin, J. P. Bird, Z. He, P. A. Bennett, and D. J. Smith, “Signatures of Quantum Transport in Self-Assembled Epitaxial Nickel Silicide Nanowires,” Appl. Phys. Lett. 85, 281-283 (2004).
3.8 Y. Chen, D. A. A. Ohlberg, G. Medeiros-Ribeiro, and Y. A. Chang, “Self-Assembled Growth of Epitaxial Erbium Disilicide Nanowires on Silicon (001),” Appl. Phys. Lett. 76, 4004-4006 (2000).
3.9 J. Nogami, B. Z. Liu, M. V. Katkov, C. Ohbuchi, and N. O. Birge, Phys. Rev. B, “Self-Assembled Rare-Earth Silicide Nanowires on Si(001),” 63, 233305 (2001).
3.10 Y. Chen, D. A. A. Ohlberg, R. S. Williams, “ Nanowires of Four Epitaxial Hexagonal Silicides Grown on Si(001),” J. Appl. Phys. 91, 3213-3218 (2002).
3.11 M. Stevens, Z. He, D.J. Smith, and P. A. Bennett, “Structure and Orientation of Epitaxial Titanium Silicide Nanowires Determined by Electron Microdiffraction,” J. Appl. Phys. 93, 5670-5674 (2003).
3.12 W. C. Yang, H. Ade, and R. J. Nemanich, “Shape Stability of TiSi2 Islands on Si(111),” J. Appl. Phys. 95, 1572-1576 (2004).
3.13 S. H. Brongersma, M. R. Castell, D. D. Perovic, and M. Zinke-Allmang, “Stress Induced Shape Transition of CoSi2 Clusters on Si(100),” Phys. Rev. Lett. 80, 3795-3798 (1998).
3.14 J. D. Carter, G. Cheng, and T. Guo, “Growth of Self-Aligned Crystalline Cobalt Silicide Nanostructures from Co Nanoparticles,” J. Phys. Chem. B, 108, 6901-6904 (2004).
3.15 Z. He, D. J. Smith, and P. A. Bennett, “Endotaxial Silicide Nanowires,” Phys. Rev. Lett. 93, 256102 (2004).
3.16 J. Tersoff and R. M. Tromp, “Shape Transition in Growth of Strained Islands: Spontaneous Formation of Quantum Wires,” Phys. Rev. Lett. 70, 2782-2785 (1993).
3.17 D. E. Jesson, G. Chen, K. M. Chen, and S. J. Pennycook, “Self-Limiting Growth of Strained Faceted Islands,” Phys. Rev. Lett. 80, 5156-5159 (1998).
3.18 C. S. Chang, C. W. Nieh, and L. J. Chen, “Formation of Epitaxial NiSi2 of Single Orientation on (111)Si inside Miniature Size Oxide Openings,” Appl. Phys. Lett. 50, 259-261 (1987).
3.19 J. Y. Yew, L. J. Chen, and K. Nakamura, “Epitaxial Growth of NiSi2 on (111)Si inside 0.1-0.6 μm Oxide Openings Prepared by Electron Beam Lithography,” Appl. Phys. Lett. 69, 999-1001 (1996).
3.20 L. J. Chen and K. N. Tu, “Epitaxial Growth of Transition Metal Silicides on Silicon,” Mater. Sci. Rep. 6 53-140 (1991).
3.21 J. M. Gibson, J. L. Bastone, R. T. Tung, and F. C. Unterwald, “Origin of A-type and B-type NiSi2 Determined by In-situ Transmission Electron Microscopy and Diffraction during Growth,” Phys. Rev. Lett. 60, 1158-1161 (1988).
3.22 P. A. Bennett, B. Ashcroft, Z. He, and R. M. Tromp, “Growth Dynamics of Titanium Silicide Nanowires Observed with Low-Energy Electron Microscopy,” J. Vac. Sci. Technol. B, 20, 2500-2504 (2002).

Chapter 4
4.1 R. K. K. Chong, M. Yeadon, W. K. Choi, E. A. Stach, and C. B. Boothroyd, “Nitride-Mediated Epitaxy of CoSi2 on Si(001),” Appl. Phys. Lett. 82, 1833-1835 (2003).
4.2 R. T. Tung, “Oxide Mediated Epitaxy of CoSi2 on Silicon,” Appl. Phys. Lett. 68, 3461-3463 (1996).
4.3 K. C. R. Chiu, J. M. Poate, J. E. Rowe, T. T. Sheng, and A. G. Gullis, “Interface and Surface Structures of Epitaxial NiSi2 Films,” Appl. Phys. Lett. 38, 988-990 (1981).
4.4 F. Edelman, E. Y. Gutmanai, A. Katz, and R. Brener, “Formation of Nickel Silicides in the Ni/Si3N4/Si System during Rapid Thermal Annealing,” Appl. Phys. Lett. 53, 1186-1188 (1988).
4.5 R. N. Ghoshtagore, “Diffusion of Nickel in Amorphous Silicon Dioxide and Silicon Nitride Films,” J. Appl. Phys. 40, 4374-4376 (1969).
4.6 L. Aballe, L. Gregoratti, A. Barinov, M. Kiskinova, T. Clausen, S. Gangopadhyay, and J. Falta, “Interfacial Interactions at Au/Si3N4/Si(111) Structures with Ultrathin Nitride Films,” Appl. Phys. Lett. 84, 5031-5033 (2004).
4.7 A. Vantomme, S. Degroote, J. Dekoster, G. Langouche, and R. Pretorius, “Concentration-Controlled Phase Selection of Silicide Formation during Reactive Deposition,” Appl. Phys. Lett. 74, 3137-3139 (1999).
4.8 C. W. Lim, C.-S. Shin, D. Gall, J. M. Zuo, I. Petrov, and J. E. Greene, “Growth of CoSi2 on Si(001) by Reactive Deposition Epitaxy,” J. Appl. Phys. 97, 044909-044914 (2005).
4.9 J. H. Lee, “Wirelike Growth of Self-Assembled Hafnium Silicides: Oxide Mediated Epitaxy,” Appl. Surf. Sci. 239, 268-272 (2005).
4.10 H. Okino, I. Matsuda, R. Hobara, Y. Hosomura, S. Hasegawa, and P. A. Bennett, “In Situ Resistance Measurements of Epitaxial Cobalt Silicide Nanowires on Si(110),” Appl. Phys. Lett. 86, 233108 1-3 (2005).
4.11 L. Zhigang, L. Shibing, W. Congshun, L. Ming, W. Wengang, H. Yilong, and Z. Xinwei, “Resistivity Measurements of Self-Assembled Epitaxially Grown Erbium Silicide Nanowires,” J. Phys. D 39, 2839-2842 (2006).
4.12 E. G. Colgan, J. P. Gambino, and Q. Z. Hong, “Formation and Stability of Silicides on Polycrystalline Silicon,” Mater. Sci. Eng. RI6, 43-96 (1996).
4.13 E. Jentzsch, R. Schad, S. Heun, and M. Huzler, “Magnetoconductivity of Thin Epitaxial NiSi2 Films in UHV at Low Temperatures,” Phys. Rev. B 44, 8984-8989 (1991).
4.14 N. M. Zimmerman, J. A. Liddle, A. E. White, and K. T. Short, “Transport in Submicrometer Buried Mesotaxial Cobalt Silicide Wires,” Appl. Phys. Lett. 62, 387-389 (1993).

Chapter 5
5.1 M. Tanaka, F. Chu, M. Shimojo, M. Takeguchi, K. Mitsuishi, and K. Furuya, “Position and Size-Controlled Fabrication of Iron Silicide Nanorods by Electron-Beam-Induced Deposition Using an Ultrahigh-Vacuum Transmission Electron Microscope,” Appl. Phys. Lett. 86, 183104 (2005).
5.2 S. Liang, R. Islam, D. J. Smith, P. A. Bennett, J. R. O'Brien, and B. Taylor, “Magnetic Iron Silicide Nanowires on Si(110),” Appl. Phys. Lett. 88, 113111 (2006).
5.3 M. V. Ivanchenko, E. A. Borisenko, V. G. Kotlyar, O. A. Utas, A. V. Zotov, A. A. Saranin, V. V. Ustinov, N. I. Solin, L. N. Romashev, and V. G. Lifshits, “Comparative STM Study of SPE Growth of FeSi2 Nanodots on Si(111)7 x 7 and Si(111)(√3x√3)-R30 Degrees-B Surfaces,” Surf. Sci. 600, 2623-2628 (2006).
5.4 K. Yamamoto, H. Kohno, S. Takeda, and S. Ichikawa, “Fabrication of Iron Silicide Nanowires from Nanowire Templates,” Appl. Phys. Lett. 89, 083107 (2006).
5.5 J. L. McChesney, A. Kirakosian, R. Bennewitz, J. N. Crainl, J.-L. Lin, and F. J. Himpsel, “Gd Disilicide Nanowires Attached to Si(111) Steps,” Nanotechnology 13, 545-548 (2002).
5.6 B. Z. Liu and J. Nogami, “Growth of Parallel Rare-Earth Silicide Nanowire Arrays on Vicinal Si(001),” Nanotechnology 14, 873-877 (2003).
5.7 H. C. Cheng, T. R. Yew, and L. J. Chen, “Interfacial Reactions of Iron Thin Films on Silicon,” J. Appl. Phys. 57, 5246-5250 (1985).
5.8 X. W. Lin, M. Behar, J. Desimoni, H. Bernas, J. Washburn, and Z. L. Weber, “Low-Temperature Ion-Induced Epitaxial Growth of -FeSi2 and cubic FeSi2 in Si,” Appl. Phys. Lett. 63, 105-107 (1993).
5.9 G. Molnar, L. Dozsa, G. Peto, Z. Vertesy, A. A. Koos, Z. E. Horvath, and E. Zsoldos, “Thickness Dependent Aggregation of Fe-Silicide Islands on Si Substrate,” Thin Solid Films 459, 48-52 (2004).
5.10 B. Egert and G. Panzner, “Bonding State of Silicon Segregated to α-Iron Surfaces and on Iron Silicide Surfaces Studied by Electron Spectroscopy,” Phys. Rev. B 29, 2091-2101 (1984).

Chapter 6
6.1 S. Y. Chen and L. J. Chen, “Nitride-Mediated Epitaxy of Self-Assembled NiSi2 Nanowires on (001)Si,” Appl. Phys. Lett. 87, 253111 (2005).
6.2 S. Y. Chen, H. C. Chen, and L. J. Chen, “Self-Assembled Endotaxial α-FeSi2 Nanowires with Length Tunability Mediated by a Thin Nitride Layer on (001)Si,” Appl. Phys. Lett. 88, 193114 (2006).

6.3 L. S. Hung, L. R. Zheng, and J. W. Mayer, “Influence of Au as an Impurity in Ni-Silicide Growth,” J. Appl. Phys. 54, 792-795 (1983).
6.4 D. Mangelinck, A. Correia, P. Gas, A. Grob, and B. Pichaud, “Gold Clusters Precipitation at the Interface between Ni(Au) Silicides and (111) Silicon,” J. Appl. Phys. 78, 1638-1642 (1995).
6.5 D. Mangelinck, P. Gas, A. Grob, B. Pichaud, and O. Thomas, “Formation of Ni Silicide from Ni(Au) Films on (111)Si,” J. Appl. Phys. 79, 4078-4086 (1996).
6.6 W. B. Pearson, in “Handbook of Lattice Spacing and Structures of Metals,” Pergamon, London, 1967, Vol. 2, p. 677.
6.7 E. I. Alessandrini, D. R. Campbell, and K. N. Tu, “Surface Reaction on MOS Structures,” J. Appl. Phys. 45, 4888-4893 (1974).
6.8 D. V. Morgan, M. J. Howes, and C. J. Madams, “Low Temperature Migration of Gold through Thin Films of Silicon Monoxide,” J. Electrochem. Soc. 123, 295-299 (1976).
6.9 T. Searle in “Properties of Amorphous Silicon and Its Alloys,” edited by T. Searle, INSPEC, London, 1998.

Chapter 8
8.1 C P. Collier, G. Mattersteig, E. W. Wong, Yi Luo, K. Beverly, J. Sampaio, F. M. Raymo, J. F. Stoddart, and J. R. Heath, “Catenane-Based Solid State Electronically Reconfigurable Switch,” Science, 289, 1172-1175 (2000).
8.2 T. Rueckes, K. Kim, E. Joselevich, G. Y. Tseng, C. Cheung, and C. M. Lieber, “Carbon Nanotube-Based Nonvolatile Random Access Memory for Molecular Computing,” Science, 289, 94-97 (2000).