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原子層沉積氮摻雜二氧化鈦薄膜之光電化學特性研究
摘要
本研究使用原子層沉積法（Atomic Layer Deposition, ALD），於300~500℃之製程溫度，以四氯化鈦（TiCl4）、氨水（ammonia water）與氨氣(NH3)混合氣體為反應前驅物在n+-Si、Cu、Ti及Ni上成長氮摻雜二氮化鈦（TiO2-xNx）薄膜，探討沉積溫度與反應氣體流量對於成長速率、結晶結構、表面形態、薄膜成份及其光電化學特性之影響。
實驗結果顯示，薄膜之成長速率在300~400℃時不受溫度影響，在450~500℃時成長速率隨溫度提高而有下降的情形；在晶體結構方面，氮摻雜會抑制rutile相形成，氨氣與水混合比例高時，只有在Ti基板上會有rutile結晶出現，其他基材上所成長之薄膜皆為anatase結晶。薄膜表面型態方面，氨與水混合比提高，晶粒有變小的趨勢。XPS能譜圖顯示氮摻雜濃度隨製程溫度或氨與水混合比提升而增加。在光電化學特性中，Si基板上沉積的N-doped TiO2隨著沉積溫度的上升及氨氣與水混合比提高，可見光的響應有一最大值，顯示著氮摻雜濃度過低時，所能激發的載子太少；過高時，載子復合率太快，導致光響應皆有降低的情形。在Cu基板上成長的N-doped TiO2比起在Si、Ti與Ni基板上有較高的可見光響應。

Photoelectrochemical properties of nitrogen-doped titanium dioxide thin films grown by atomic layer deposition
Abstract
In this study, N-doped titanium dioxide (TiO2) films were grown on n+-Si, Ti, Ni and Cu by atomic layer deposition at 300~500℃ with TiCl4 precursor and a mixture of H2O and NH3 gases. The effects of NH3-to-H2O ratio and deposition temperature on the film properties were investigated. The surface morphology, crystal structure, and photocurrent of N-doped TiO2 films were characterized by using SEM, XRD , and Potentiostat, respectively.
The results show that the growth rate was independent of deposition temperature at temperatures between 300 and 400℃, but it decreased with the increase of deposition temperature at temperatures between 450 and 500℃. The XRD patterns demonstrated that the crystalline form was anatase for films grown on Si, Ni and Cu substrates at temperatures between 300℃ and 500℃ with a high NH3-to-H2O ratio. As lowering the NH3-to-H2O ratio, the crystalline from become a mixture of anatase and rutile for films grown at temperatures between 350℃ and 450℃. According to SEM images, the change of grain size with process temperature was insignificant. The nitrogen incorporation was confirmed by XPS. The visible-light photocurrent of as-deposited N-doped TiO2 films had a maximum with deposition temperature and NH3-to-H2O ratio. The N-doped TiO2 films grown on Cu substrates had higher visible-light photocurrent than those grown on Si, Ti, and Ni substrates.

目　　錄

中文摘要…………………………………………………………………………………i
英文摘要…………………………………………………………………………………ii
誌謝………………………………………………………………………………………iii
目錄………………………………………………………………………………………iv
圖目錄……………………………………………………………………………………v
表目錄……………………………………………………………………………………viii
第一章 前言……..……………………………………………………………………1
第二章 理論及文獻回顧………………………………………………………………5
2-1 二氧化鈦的結構與性質……………………………………………………5
2-2 光觸媒之氧化還原原理 ……………………………………………………7
2-3 原子層沉積法理論基礎……………………………………………………10
2-4氮摻雜TiO2文獻回顧 ………………………………………………………13
第三章 實驗步驟………………………………………………………………………16
3-1實驗流程規劃…………………………………………………………………16
3-2 ALD- TiO2系統設計………………………………………………………17
3-3 材料準備……………………………………………………………………21
3-4薄膜量測與分析………………………………………………………………22
第四章 結果與討論……………………………………………………………………27
4-1沉積條件對ALD TiO2薄膜特性之影響……………………………………27
4-1-1沉積溫度之影響……………………………………………………27
4-1-2反應氣體流量之影響………………………………………………42
4-2基材種類對ALD N-doped TiO2特性之影響………………………………50

第五章 總結論…………………………………………………………………………55
參考文獻…………………………………………………………………………………56

參考文獻
[1] A. Fujishima, K. Honda,”Electrochemical Photolysis of Water at a Semiconductor Electrode”, Nature 238 (1972) 37-38
[2] M.I. Litter,”Heterogeneous photocatalysis Transition metal ions in photocatalytic systems”, Applied Catalysis B, 23 (1999) 89-114.
[3] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga,”Visible-light photocatalysis in nitrogen-doped titanium oxides”, Science, 293 (2001) 269.
[4] 鄭光煒,”The application of photocatalyst in energy and environmental era”, 新型奈米可見光光觸媒開發現況與應用趨勢研討會講稿, 崑山科技大學, 民國 93年 10月。
[5] 掌軒, “以低溫燒結法製作二氧化鈦光觸媒薄膜的探討” ,元智大學九十三學年化工系碩士論文.
[6] 楊敏麒,楊天賜,徐上鋒,陳文泰,翁明壽, “Photocatalytic properties of the C-doped titanium oxide films byion-assisted electron beam evaporation” ,2004材料年會論文集,編號P-171.
[7] 詹光達,”二氧化鈦薄膜的製備與量測” ,逢甲大學九十三學年光電物理研究所碩士論文.
[8] 周宏邦,”濺鍍二氧化鈦與氮摻雜二氧化鈦薄膜之結構與光觸媒性質研究” ,國立東華大學九十三學年材料科學與工程學系碩士論文.
[9] 吳怡玲,”以化學氣相沈積法製備二氧化鈦光觸媒之研究” ,國立中興大學八十九學年環工系碩士論文.
[10] M. Leskela, M. Ritala,”Atomic layer deposition (ALD): from precursors to thin film structures”, Thin Solid Films, 409 (2002) 138-146.
[11]羅幼旭,”TiO2奈米多孔性薄膜於染料敏化太陽能電池之應用” ,實驗課程講義.
[12] F. Zhang, N. Huang, P. Yang, et al., “Blood compatibility of titanium oxide prepared by ion-beam-enhanced deposition”, Surf. Coat. Technol. 84 (1996) 476–479
[13] M. Bekholet, “Photocatalytic bactericidal activity of TiO2 in aqueous suspensions of E. coli”, Water Science and Technology, 35:11-12 (1997) 95-100.
[14] K. Sunda, Y. Kikuchi, K. Hashimoto, and A. Fujishima,”Bactericidal and Detoxification Effects of TiO2 Thin Film Photocatalysts”, Environmental Science and Technology 32:5 (1998) 726-728.
[15] M. Schiavello,”Heterogeneous Photocatalysis”, Willey, (1997) 103-117.
[16] T. Tanaka, T. Lto, S. Takenaka, “Photocatalytic oxidation of alkane at a steady
rate over alkali-ion-modified vanadium oxide supported on silica”, Catalysis
Today, 61 (2000) 109-115.
[17] 黃耀輝, “光觸媒降解水污染物應用”,2004奈米實作研習營,南區奈米科技K-12教育發展中心.
[18] C. He, Y. Yu, X. Hu and A. Larbot, “ Influence of silver doping on the photocatalytic activity of titania films “,Applied Surface Science, 200 (2002) 239-247,
[19] M. K. Gobbert, V. Prasad, T. S. Cale, “Predictive modeling of atomic layer deposition on the feature scale”, Thin Solid Films, 410 (2002) 129.
[20] M. Ritala, M. Leskela, J. P. Dekker, C. Mutsaers, P. J. Soininen, and J. Skarp, “Perfectly conformal TiN and Al2O3 films deposited by atomic layer deposition”, Chem. Vap. Deposition, 5 (1999) 7.
[21] M. Ritala, M. Leskela, E. Rauhala, and J. Jokinen, “Atomic layer epitaxy growth of TiN thin films from TiI4 and NH3”, J. Electrochem. Soc., 145 (1998) 2914.
[22] T. Suntola, Atomic layer epitaxy, in Handbook of Crystal Growth, Ed. D. T. J. Hurle, Vol. 3, Thin Films and Epitaxy, Part B: Growth Mechanisms and Dynamics, Elsevier, Amsterdam (1994), Ch. 14.
[23] M. Putkonen, “Development of low-temperature deposition processes by atomic layer epitaxy for binary and ternary oxide thin films”, Dissertation for PhD., department of chemical technology, Helsinki University of Technology, Espoo 2002, Finland.
[24] V. Pore, M. Heikkila, M. Ritala, M. Leskela, S. Areva, “Atomic layer deposition of TiO2-XNX thin films for photocatalytic applications”, Journal of Photochemistry and Photobiology A: Chemistry 177 (2006) 68-75.
[25] G. Liu, X. Wang, Z. Chen, H. M. Cheng, G. Q. (MAX) Lu, “The role of crystal phase in determining photocatalytic activity”, Journal of colloid and Interface Science 329 (2009) 331-338
[26] Perkin-Elmer ESCA Manual, Version 3.0 (Perkin-Elmer,Eden Prairie, MN, 1991)
[27] N. C. Saha, H. G. Tompkins, “Titanium nitride oxidation chemistry: An x-ray photoelectron spectroscopy study”, Journal of Applied Physics 72 (1992) 3072-3079.
[28] G. R. Torres, T. Lindgren, J. Lu, C. G. Granqvist, S. E. Lindquist, “Photoelectrochemical Study of Nitrogen-Doped Titanium for Water Oxidation”, Journal of Physical Chemistry B 108 (2004) 5995-6003