臺灣博碩士論文加值系統

本論文之研究方向是以化學氣相沉積法來製備FeSi和β-FeSi2奈米線並探討其生長機制及成長參數對形貌之影響，另外提出兩種方法做為奈米線之形貌改良，並對形貌改良前後之奈米線做性質比較。
在成長參數的部分，本實驗分別以溫度與持溫時間，流量和沉積位置，以及壓力三部份來探討。發現實驗溫度從750℃開始上升至850℃時β-FeSi2有奈米線之生成，但是到了950℃即有團塊化的行為，其原因為奈米線生長到後期互相反應的結果。在流量和沉積位置則是以氧化鋁基板在不同的流量和位置上進行沉積，用EDX分析基板上的反應物訊號來確定反應物濃度分佈。在不同壓力的實驗則是利用CS(Covered-substrate)的方法來分析高壓下奈米線線徑增加的原因，並在高溫高壓的環境下成長出FeSi奈米線。
形貌改良則是以Pre-Deposition和Covered-substrate來對奈米線進行形貌改良，以不使用催化劑或是模板的方式，單純控制成長參數來成長奈米線陣列，最後分別比較改良前後奈米線之磁性以及場發射性質。

In this thesis, we synthesized β-FeSi2 and FeSi nanowires by chemical vapor deposition (CVD). The effect of CVD parameters including temperature, flow rate, during time, working pressure and deposition position in the growth of nanowires have been investigated and we consider all the CVD parameters would affect the supersaturation in the tube furnace. FeSi nanowires were gown under high supersaturation and β-FeSi2 nanowires were grown under low supersaturation. In the morphology improvement, two methods, “Pre-deposition method” and “Covered substrate method” were used to deposit nanowire arrays. “Pre-deposition method” could form heterogenerous nucleation sites on the surface of thin film. “Coverer substrate method” is that one substrate is covered by the other substrate. In the interlayer between two substrates, the flow direction is uniform and that would help to grow nanowire arrays. The reaction concentration would decrease from boundary of substrate to the middle and the concentration distribution on the substrate caused different nanostructure. In the property measurement, the magnetic property and field emission property were measured by SQUID and field emission measurement system with Keithley-237. The morphology-improved nanowires have better magnetic properties and field emission properties.

中文摘要 I
Extend Abstract II
誌謝 IX
第一章 前言 1
第二章 文獻回顧 2
2-1奈米科技 2
2-2奈米線的成長方法 4
2-2-1 氣液固成長機制-Vapor-liquid-solid(VLS) methods 4
2-2-2 水溶液法-Solution methods 6
2-2-4 分子束磊晶成長-Metal catalyzed molecular-beam epitaxy 8
2-2-4 雷射輔助法-Laser-assisted growth 10
2-2-5 熱蒸氣法-Thermal evaporation 11
2-3 Fe-Si系統和CVD的成長參數以及機制 13
第三章 實驗方法與步驟 25
3-1 實驗流程 25
3-2 實驗步驟 25
3-2-1 成長β-FeSi2和FeSi的奈米線 25
3-2-2 退火實驗 27
3-2-3 形貌改良 27
3-2-4 性質量測 28
3-3 實驗儀器 30
3-3-1 薄膜X光繞射分析儀(Thin FilmX-Ray Diffractometer, XRD) 30
3-3-2 掃描式電子顯微鏡(Scanning Electron Microscopy, SEM) 31
3-3-3 穿透式電子顯微鏡(Transmission Electron Microscopy, TEM) 31
3-3-4 超導量子干涉儀 34
3-3-5 場發量測系統 34
第四章 結果與討論 36
4-1 成長參數對成分以及形貌的影響 36
4-1-1載流氣體流量和試片位置的影響 36
4-1-2 溫度和持溫時間的影響 45
4-1-3壓力的影響 53
4-1-4 奈米線成長機制 62
4-2 退火實驗 70
4-2-1奈米線的退火 70
4-2-2薄膜的退火 74
4-3 形貌改良 79
4-3-1預沉積法(Pre-deposition) 79
4-3-2 基板覆蓋法(Covered Substrate Method) 89
4-4 性質量測 103
4-4-1 磁性分析 103
4-4-2 場發性質量測 105
第五章 結論 109
參考文獻 110

[1]R.S. Wagner, W.C. Ellis, Appl. Phys. Lett. Vol.4, p.89. (1964)
[2]Chia Ying Lee,Tseung Yuen Tseng,Seu Yi Li and Pang Lin Tamkang, Journal of Science and Engineering, Vol.6, No.2, p.127-132. (2003)
[3]J. Bauer, V. Gottschalch, H. Paetzelt, G. Wagner, Journal of Crystal Growth, Volume 310, Issue 23, p.5106-5110. (2008)
[4]Zhu, Y.Q. Journal of Materials Chemistry. p.1859-1864. (1998)
[5]Liu, Z.Q. Journal of Materials Research.Vol.16, pp.683-686. (2001)
[6]Grap T, Rieger T, Blömers Ch, Schäpers T, Grützmacher D, Lepsa MI, Nanotechnology. (2013)
[7]Sun, Y.; Fuge, G. M.; Fox, N. A.; Riley, D. J.; Ashfold, M. N. R. Adv.Mater, pp.2477-2481. (2005)
[8]L. Schubert, P. Werner, N.D. Zakharov, G. Gerth, F.M. Kolb, L. Long, U.Go¨sele, Appl. Phys. Lett. Vol.84. (2004)
[9]M.T. Bjo¨rk, B.J. Ohlsson, T. Sass, A.I. Persson, C. Thelander, M.H.Magnusson, K. Deppert, L.R. Wallenberg, L. Samuelson, Appl. Phys.Lett. Vol.80, p.1058. (2002)
[10]A.P. Levitt, Whisker Technology, John Wiley ＆ Sons Inc. (1971)
[11]Y.F. Zhang, Y.H. Tang, X.F. Duan, Y. Zhang, C.S. Lee, N. Wang, I. Bello, S.T. Lee, Chem. Phys. Lett. 323, p180. (2002)
[12]T.J. Trentler, K.M. Hickman, S.C. Goel, A.M. Viano, P.C. Gibbons and W.E. Buhro, Science, vol.270, p.1791. (1990)
[13]N.E. Christensen, Phys.Rev.B, Vol.42, p.7148-7153. (1990)
[14]M. Alexe, V.Dragoi, M.Reiche, Electron. Lett. 36, p.677. (2000)
[15]Takashi, Suemasu, J. Appl. phys vol.39. (2000)
[16]T.Suemasu, Thin Solid Films, Vol.461, p.209-218. (2004)
[17]V.Cronin, Handbook of Thermoelectrics, Press London. (1995)
[18]R.Ware and D.J.Mcneill,Proc.Inst. Electr. Eng.Vol.111, p178. (1964)
[19]Mikio Ito, Hiroshi Nagai, Etsushi Oda, J.Appl.Phys.Vol.91, p2138. (2002)
[20]D.Leong, M. Harry, K.Reeson, and K.Homewood, Nature 387, p.686. (1997).
[21]Nagai H, Katsuyama S, Nakayama S, Kobayashi H, Majima K, Ito M, Materials Transactions, JIM, Vol.39,No.4,p.515-521. (1998)
[22]Yamaguchi K, Heya A, Shimura K, Katsumata T, Yamamoto H,Hojou K. Thin Solid Films ,Vol.461, p.17-21. (2004)
[23]Wang JF, Ji SY, Mimura K, Sato Y, Song SH, Yamane H, Shimada M, Isshiki M, Phys Stat Sol A , Vol.201, p2905–2909. (2004)
[24]Naito M, Ishimaru M, “Formation process of beta-FeSi2 from amorphous Fe-Si synthesized by ion implantation: Fe concentration dependence. J Microsc, 236, p.123-127. (2009)
[25]Mahan JE, Geib KM, Robinson GY, Long RG, Xinghua Y, Bai G, Nicolet M, Nathan M, “Epitaxial films of semiconducting beta- FeSi2 on (001) silicon. Appl Phys Lett, 56, p.2126-2128. (1991)
[26]Shih-Wei Hung, Ping-Hung Yeh. J.Mater.Chem, 21, p.5704. (2011)
[27]S. J. Clark, H. M. Al-Allak, S. Brand and R. A. Abram,Phys. Rev. B: Condens. Matter, 58, p10389. (1998)
[28]D. B. Migas and L. Miglio, Phys. Rev. B: Condens. Matter, p.62. (2000)
[29]L. J. Chen, S. Y. Chen and H. C. Chen, Thin Solid Films, 515, p.8140. (2007)
[30]J.F. Wang, Journal of Crystal Growth 295, p129–132. (2006)
[31]“Role of Carrier Gas Flow and Species Diffusion in Nanowire Growth from Thermal CVD, Andreas Menzel, Raya GoldbergJ. Phys. Chem. C, 116, p.5524-5530. (2012)
[32]Colli, A.; Fasoli, A.; Hofmann, S.; Ducati, C.; Robertson, J.Ferrari, Nanotechnology, 17, p1046. (2006)
[33]Xiangdong Li, Guowen Meng, Qiaoling Xu, Nano Lett, Vol.11, p.1704-1709. (2011)
[34]X光繞射原理及其應用,83年6月,工業材料86期,林麗娟
[35]Eidgenössische Technische Hochschule Zürich-Electron microscopy site, F.Krumeich, Vol.11. (2012)
[36] “Synthesis and properties of single-crystalline β-FeSi2 nanowires, J.Y. YANG. (2013)
[37]Florian Dhalluin, Pierre J. Desre, Martein I, Journal of Applied Physics, Vol.102. (2007)
[38]J.Johansson, CPT.Svensson, T.Martensson, L.Samuelson, and W Seifert, J. Phys. Chem. B.109, Vol.28, p.13567-13571. (2005)
[39]L.Ratke P.W.Voorhees, New York, p.117-124. (2002)
[40]H. Yamane, T. Yamada, Journal of Alloys and Compounds, 476, p.282-287. (2009)
[41]Dy.Er, Fr-Mo, Landolt-Börnstein, Group IV Physical Chemistry Volume 5e, p.1-6. (1995)
[42]Hailong Wang, Luis A. Zepeda-Ruiz, George H. Gilmer, Moneesh Upmanyu, NATURE COMMUNICATIONS. (1956)
[43]E.I. Givargizov, Springer, New York. (1987)
[44]E.I. Givargizov, A.A. Chernov, Sov. Phys. Crystallogr 18, 89. (1973)
[45]Jun-Ku Ahn, Kyoung-Woo Park, Hyun-June Jung and Soon-Gil Yoon, Nano Lett. Vol.10, p.472-477. (2010)
[46]L.E. Wilson, N.W. Gregory, J.Phys.Chem, 62, p.433. (1958)
[47]Magnus, T. Borgstro¨M, George Immink, Bas Ketelaars, Rienk Algra, and Eric P.A.M. Bakkers, nature nanotechnology, vol 2. (2007)
[48]Jiang Yanfeng, Zhang Yamin, Journal of Semiconductors, Vol. 31, No. 1. (2010)
[49]Davide Barreca, Daniela Bekermann, Elisabetta Comini, Anjana Devi, Roland A. Fischer, The Royal Society of Chemistry, 12, p.3419-3421. (2010)
[50]Zhanjun Gu,M. Parans Paranthaman, Jun Xu,and Zheng Wei Pan,Acsnano, Vol. 3,2, pp.273-278. (2009)
[51]Peng Yu, Xiong Zhang, Dongliang Wang, Lei Wang, and Yanwei Ma, American Chemical Society. (2009)
[52]Richard Ritikos ,Muhamad Rasat Muhamad, Saadah Abdul Rahman , Siti Meriam Ab. Gani , Yoke Khin Yap, CARBON, 49, p.1842-1848. (2011)
[53]Hao Chen, Ajit Roy, Jong-Beom Baek, Lin Zhu, Liming Dai, Jia Qu, Materials Science and Engineering, Vol.70, p.63-91. (2007)
[54]Jiangni Yun, Rui Qu, Zhiyong Zhang, and Jun Li, Hindawi, Advances in Condensed Matter Physics. (2014)
[55]Y.Y.Chen, P.C.Lee, C.B.Tsai, and Neeleshwar, J.Appl. Phys.Vol.91, 251907. (2007)