本研究成功利用不同前趨物，以溶膠凝膠法與水熱法之合成方法 製備出兩系列TiO2:Eu3+工作電極材料( TBT 與 P25)，以 XRD 等量測 進行材料結構鑑定分析，並探討Eu 摻雜後對於 TiO2之發光特性與電 子組態之影響，爾後將材料應用於敏化太陽能電池之工作電極，研究 修飾後之TiO2電極對於電池效率之影響，其重要結果如下：
(a)本研究以溶膠凝膠法及水熱法藉由 Eu 摻雜成功合成出純銳鈦礦 (Anatase)之二氧化鈦。並且由於 Eu-Ti-O 鍵結形成，不僅延緩金紅 石(Rutile)晶相生成，有較好之光電特性，亦限制晶體之成長，由於 粒徑越小增加其比表面積，因此有效提升太陽能電池染料之吸附 量，增加電池之效率表現。
(b)以光激發光譜分析樣品得知，隨著活化劑 Eu 摻雜量之增加，主體 晶格 TiO2 之發光強度隨之增加，於高濃度出現濃度淬滅現象。而 拉曼光譜亦證實藉由Eu 摻雜成功延遲煆燒過程中金紅石(Rutile)晶 相生成，且增加粉體表面之氧空缺。
(c)本研究以紫外-可見光擴散式反射光譜測量 TiO2:Eu3+之吸收特性，
經由 Eu 摻雜後出現之紅位移現象，顯示 TiO2 於摻雜稀土金屬離 子產生能階混成，造成能隙縮小增加對於可見光範圍之吸收；並以 X 射線光電子能譜儀分析獲知摻雜離子 Eu3+於晶體中位置，並以價 帶光譜之量測，成功建立樣品之價帶傳導帶能階位置。而 X-光吸 收光譜之近邊緣光譜分析得知，Eu 摻雜後鍵結中電子轉移造成表 面氧空缺增加。
(d)將合成之材料應用於染料敏化太陽能電池之工作電極，本研究原 構想欲透過發紅光之TiO2:Eu3+，以增加染料Black dye 於紅光波段
之利用，然而由光電特性卻發現，由於摻雜後氧空缺所造成之雜質 態捕捉光電子，由光電流降低之現象證實光電子量減少。
(e)為提高染料敏化電池效率，本研究利用雙層結構工作電極之設計而 形成階梯式位階排列，不僅增加傳遞驅動力，亦由於電極屏障生成 以減少電子再復合之機率，而短路電流之增加證實此點，並透過與 染料能階之混成，提高開路電壓值，因此整體結果提高電池之效 率。而將染料製換為硒化鎘(CdSe)量子點作為敏化物，第二層為 Eu 摻雜材料之電池，效率亦明顯提升，進一步證實此研究構想之 正確性。
總而言之，本研究合成兩系列 TiO2:Eu3+樣品並探討其之晶體 結構特性，發光性質以及建立摻雜離子 Eu3+對於其電子組態之影 響，且透過雙層結構設計，成功提高敏化太陽能電池之效率。
參考文獻
1. 許志偉, 陳宏仁, 林怡君 and 王立義, 有機/無機太陽能電池之 現況發展, 化工, 第52卷, 第2期, 49-58, 民94.
2. A.J. McEvoy and M. Gritzel, Sol. Energ. Mat. Sol. C, 1994, 32, 3, 221.
3. A. Hagfeldt, B. Didriksson, T. Palmquist, H. Lindström, S. Södergren, H. Rensmo and S.E. Lindquist, Sol. Energ. Mat. Sol. C, 1994, 31, 481.
4. B. O’Regan and M. Grätzel, Nature, 1991, 353, 737.
5. M. Grätzel, Nature, 2001, 414, 338.
6. 黃建昇, 結晶矽太陽電池發展近況, 工業材料雜誌, 第203期, 150, 民92.
7. http://cdnet.stpi.org.tw/techroom/market/energy/energy022.htm, 國 家實驗研究院科技政策研究與資訊中心(Science & Technology Policy Research and Information Center，STPI).
8. M. Grätzel, Phil. Trans. R. Soc. A, 2007, 365, 993.
9. X. Chen and S.S. Mao, Chem. Rev, 2007, 107, 2891.
10. D. Cahen, G. Hodes, M. Grätzel, J.F. Guillemoles and I. Riess, J.
Phys. Chem. B, 2000, 104, 2053.
11. D. Matthews, P. Infelta and M. Grätzel, Sol. Energ. Mat. Sol. C, 1996, 44, 119.
12. M. Grätzel, J. Photochem. Photobio. A, 2004, 164, 3.
13. T.N. Rao and L.J. Bahadur, J. Electrochem. Soc, 1997, 144, 179.
14. A.B. Kashyout, M. Soliman and M. Fathy, Mater. Chem. Phys, 2005, 90, 230.
15. P. Guo and M.A. Aegerter, Thin Solid Films, 1999, 351, 290.
16. K. Sayama, H. Sugihara and H. Arakawa, Chem. Mater, 1998, 10, 3825.
17. B.V. Bergeron, A. Marton, G. Oskam and G.J. Meyer, J. Phys. Chem.
B, 2005, 109, 793.
18. S. Chappel and A. Zaban, Sol. Energ. Mat. Sol. C, 2002, 71, 141.
19. K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara and H.
Arakawa, Sol. Energ. Mat. Sol. C, 2000, 115, 64.
20. B. Tan, E. Toman, Y. Li and Y.Y. Wu, J. Am. Chem. Soc, 2007, 129, 463.
21. C.J. Barbé, F. Arendse, P. Comte, M. Jirousek, F. Lenzmann, V.
Shklover and M. Grätzel, J. Am. Ceram. Soc, 1997, 80, 3157.
22. K. Kalyanasundaram and M. Grätzel, Coord. Chem. rev, 1998, 177, 347.
23. N.G. Park, J.V.D. Lagemaat and A.J. Frank, J. Phys. Chem. B, 2000, 104, 989.
24. M.K. Nazeeruddin, A. Kay, I. Rodicio, R.H. Baker, E. Müller, P.
Liska, N. Vlachopoulos and M. Grätzel, J. Am. Chem. Soc, 1993, 115, 6382.
25. G. P. Smestad and M. Grätzel, J. Chem. Educ, 1998, 75, 752.
26. 劉茂煌﹐奈米光電池﹐工業材料雜誌, 2003﹐203 期, 民93.
27. M.K. Nazeeruddin, S.M. Zakeeruddi, R.H. Baker, M. Jirouse, P. Lisk, N. Vlachopoulos, V. Shklover, C.H. Fischer and M. Grätzel﹐Inog.
Chem, 1999﹐38﹐6298.
28. K.S. Finnie, J.R. Bartlett and J.L. Woolfrey, Langmuir, 1998, 14, 2744.
29. C. Bauer, G. Boschloo, E. Mukhtar and A. Hagfeldt﹐J. Phys.Cem. B, 2002, 106, 12693.
30. C.G. Garcia, N.Y.M. Iha, R. Argazzi and C.A Bignozzi, Inorg. Chem, 1994, 33, 5741.
31. M.K. Nazeeruddin, M. Amirnasr, P. Comte, J.R. Mackay, A.J.
McQuillan, R. Houriet and M. Gratzel, Langmuir, 2000, 16, 8525.
32. M.K. Nazeeruddin, P. Péchy, T. Renouard, S.M. Zakeeruddin, R. H.
Baker, P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover, L.
Spiccia, G.B. Deacon, C.A. Bignozzi and M. Grätzel, J. Am. Chem.
Soc, 2001, 123, 1613.
33. J. Hagaen, W. Schaffrath, P. Otschik, R. Fink, A. Bacher, H.W.
Schmidt and D. Haarer, Synthetic. Met, 1997, 89, 215.
34. N. Papageorgiou, W.F. Maier and M. Grätzel, J. Electrochem. Soc, 1997, 144, 876.
35. A. Kay and M. Grätzel, Sol. Energ. Mat. Sol. C, 1996, 44, 99.
36. S. Chen, S.K. Deb and H. Witzke, U.S Patent, 1978, 4,080,488, March 21.
37. M. Grätzel and K. Kalyanasundaram, Curr. SCi, 1994, 66, 706.
38. M.K. Nazeeruddin, A. Kay, I. Rodicio, R, Humphry-Baker, E.
Müller, P. Liska, N. Vlachopoulos and M. Grätzel, J. Am. Chem.
Soc, 1993, 115, 6382.
39. M. Grätzel, AIP Conf. Proc, 1997, 404, 119.
40. M. Grätzel, J. Photo. Photobio. A: Chem, 2004, 164, 3.
41. L. Han, Y. Chiba and A. Islam, 16th International Conference of Photochemical Conversion and Solar Sstorage. Uppsala, Sweden, 2006.
42. Y. Chiba, A. Islam and Y. Watanabe, J. Appl. Phys, 2006, 45, 638.
43. M.K. Nazeeruddin, F.D. Angelis and S. Fantacci, J. Am. Chem. Soc, 2005, 127, 16835.
44. J.M. Kroon, N.J. Bakker, H.J.P. Smit, P. Liska, K.R. Thampi, P.
Wang, S.M. Zakeeruddin, M. Gratzel, A. Hinsch, S. Hore, U. Wurfel, R. Sastrawan, J.R. Durrant, E. Palomares, H. Pettersson, T.
Gruszecki, J. Walter, K. Skupien and G.E. Tulloch, Prog. Photovolt:
Res. Appl.
45. H. Arakawa, T. Yamaguchi and A. Takeuchi, 16th International Conference of Photochemical Conversion and Solar Storage, Uppsala, Sweden, 2006. W42P210.
46. M. Spath, J.V. Roosmalen and P. Sommeling, 3rd WCPEC. Osaka , Japan, 2003.
47. H. Tsubomura, M. Matsumura, Y. Nomura and T. Amamiya, Nature, 1976, 261, 402.
48. P.M. Sommeling, 2nd WCPEC, Vienna, 1998.
49. C.J. Barbe, J. Am. Cera. Soc, 1997, 80, 3157.
50. K. Tennakone, J. Phys. D: Appl. Phys, 1998, 31, 1492.
51. M.K. Nazeeruddin, P. Pĕchy and M. Grätzel, Chem. Comm, 1997, 36, 1705,
57. L. Vlachopouios, J. Am. Chem. Soc, 1988, 110, 1216.
58. V. Vamathevan, H. Tse, R. Amala, G. Lowb and S. McEvoy, Catalysis Today, 2002, 68, 201.
59. M.I. Litter and J.A. Navio, J. Photo. Photobio. A: Chem, 1996, 98, 171.
60. J. Yu, H. Yu, C.H. Ao, S.C. Lee, J.C. Yu and W. Ho, Thin Solid Films, 1999, 496, 273.
61. W. Li, Y. Wang, H. Lin, S.I. Shah, C.P. Huang, D.J. Doren, S.A.
Rykov, J.G. Chen and M.A. Barteau, Appl. Phys. Lett, 2003, 83, 20.
62. R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki and Y. Taga, Science, 2001, 293, 269.
63. C. Jia, E. Xie, A. Peng, R. Jiang, F. Ye, H. Lin and T. Xu, Thin Solid Films, 2006, 496, 555.
64. M. Saif and M.S.A. Abdel-Mottaleb, Inorg. Chem. Acta, 2007, 360, 2863.
65. 湯友聖, 台灣師範大學碩士論文, 臺北, 民 97.
66. R.C. Ropp, Luminescence and the Solid State, Elservier, Amsterdam, 2004.
67. H. Dieke and R.A. Satten, Am. J. Phys, 1970, 38, 399.
68. http://cai.wit.edu.cn/mse/liuyu2006ppt/liuX-ray.ppt.
69. A.R. West, Basic Solid State Chemistry, John Wiley & Sons, Singapore, 1991.
70. 吳泰伯 and 許樹恩, X-光繞射原理與材料結構分析, 國科會精儀 中心, 台北, 民 82.
71. http://www.ndhu.edu.tw/~nano/labtext/93_Ma_II_v2.pdf.
72. 林群哲, 台灣大學化學所碩士論文, 臺北, 民 96.
73. 賴泓均, 台灣大學化學所碩士論文, 臺北, 民 95.
74. S. Ito, T.N. Murakami, P. Comte, P. Liska, C. Grätzel, M.K.
Nazeeruddin and M. Grätzel, Thin Solid Films, 2008, 516, 4613.
75. H. Kusama , M. Kurashige, K. Sayama, M. Yanagida and Hideki.
Sugihara, J. Photochem. Photobio. A, 2007, 189, 100.
76. 蕭光宏, 台灣大學化學所碩士論文, 臺北, 民 97.
77. Y. Yoshida, S. Tokashiki, K. Kubota, R. Shiratuchi, Y. Yamaguchi, M. Kono and S. Hayase, Sol. Energ. Mat. Sol. C, 2008, 92, 646.
78. J.J. Wu, G.R. Chen, H.H. Yang, C.H. Ku and J.Y. Lai, Appl. Phys.
Lett, 2007, 90, 213109.
79. M. Adachi, M. Sakamoto, J. Jiu, Y. Ogata and S. Isoda, J. Phys.
Chem. B, 2006, 110, 13872.
80. J. Lin and J.C. Yu, J. Photochem. Photobiol. A: Chem, 1998, 116, 63.
81. T. Lindgren, J.M. Mwabora, E. Avendano, J. Jonsson, A. Hoel, C.G.
Granqvist and S.E. Lindquist, J. Phys. Chem. B, 2003, 107, 5709.
82. H. Tang, H. Berger, P.E. Schimid, F. Levy and G. Burri, Solid. State.
Commun, 1993, 87, 847.
83. G. Oskam, A. Nellore, R.L. Penn and P.C. Searson, J. Phys. Chem. B, 2003, 107, 1734.
84. M.A. Anderson, M.J. Gieselmann, Q. Xu, J. Membr. Sci, 1988, 39, 243.
85. P. Ganguly, N. Shah, M. Phadke, V. Ramaswamy, I.S. Mulla, Phys.
Rev. B, 1993, 47, 991.
86. J.H. Li, W.L. Kang, W.H. Yan, Y.H. Guo, H.F. Gao and Z.H. Liu, Acta. Phys. Chim. Sin, 2008, 24, 1030.
87. N.G. Park, J.V.D. Lagemaat and A.J. Frank, J. Phys. Chem. B, 2000, 104, 8989.
88. R.A. Spurr and H. Myers, Anal. Chem, 1957, 29, 760.
89. S. Yin, H. Yamaki, M. Komatsu, Q Zhang, J Wang, Q. Tang, F. Saito and T. Sato, J. Mater. Chem, 2003, 13, 2996.
90. E. Setiawati and K. Kawano, J. Alloy. Compd, 2008, 451, 293.
91. B. Zou, L. Xiao, T. Li, J. Zhao, Z. Lai and S. Gu, Appl. Phys. Lett, 1991, 59, 1826.
92. J. Yang, Z.W. Quan, D.Y. Kong, X.M. Liu and J. Lin, Cryst. Growth.
Des, 2007, 7, 730.
93. T. Hirai and Y. Kondo, J. Phys. Chem. C, 2007, 111, 168.
94. S. Yan, J. Zhang, X. Zhang, S. Lu, X. Ren, Z. Nie and X. Wang, J.
Phys. Chem. C, 2007, 111, 13256.
95. G. Blasse and B.C. Grabmaier, Luminescence Materials, Chap. 9, 186.
96. T. Miyakawa and D. L. Dexter, Phys. Rev. B, 1970, 1, 2961.
97. K.L. Frindell, M.H. Bartl, M.R. Robinson, G.C. Bazan, A. Popitsch and G.D. Stucky, J. Solid. State. Chem, 2003, 172, 81.
98. D.L. Dexter, J.H. Schulman, J. Chem. Phys, 1954, 22, 1063.
99. T. Blasse, G. Philips Res. Rep, 1969, 24, 131.
100. L. Ozawa and P.M. Jaffe, J. Electrochem. Soc, 1971, 118, 1678.
101. Q.Z. Wang, J. Tian, X.H. Yang and X. Gao, J. Chin. Lumin, 1995, 16, 57.
102. Y.H. Zhang, C.K. Chan, J. Porter and W. Guo, J. Mater. Res, 1998, 13, 2602.
103. B.D. Yao, Y.F. Chan, X.Y. Zhang, W.F. Zhang, Z.Y. Yang and N.
Wang, Appl. Phys. Lett, 1998, 82, 281.
104. D. Bersani, P.P. Lottic and X.Z. Ding, Appl . Phys. Lett, 1998, 72, 1.
105. Y.L. Li and T. Ishigaki, J. Phys. Chem. B, 2004, 108, 15536.
106. J.C. Parker, R.W. Siegel, J. Mater. Res.1990, 5, 1246.
107. H.C. Choi, Y.M. Jung and S.B. Kim, Vib. Spectrosc, 2005, 37, 33.
108. J.G Li, X. Wang, K. Watanabe and T. Ishigaki, J. Phys. Chem. B, 2006, 110, 1121.
109. T. Sreethawong, Y. Suzuki, S. Yoshikawa, Int J Hydrogen Energ, 2005, 30, 1053.
110. M. Saif and A. Mottaleb, Inorg. Chem. Acta, 2007, 360, 2863.
111. S. Rengaraj, X.Z. Li, P.A. Tanner, Z.F. Pan and G.K.H. Pang, J. Mol.
Catal. A: Chem, 2005, 247, 36.
112. A.B. Murphy, Appl. Opt, 2007, 46, 3133.
113. P. Kubelka, J. Opt. Soc. Am, 1948, 28, 448.
114. D.G. Barton, M. Shtein, R.D. Wilson, S.L. Soled and E. Iglesia, J.
Phys. Chem. B, 1999, 103, 630.
115. P.A. Tanner, K.L. Wong and Y. Liang, Chem. Phys. Lett, 2004, 399, 15.
116. T. Umebayashi, T. Yamaki, H. Itoh and K.J. Asai, Phys. Chem. Solid, 2002, 63, 1909.
Magn. Magn. Mater, 2002, 251, 245.
120. W. Gopel, Surf. Sci, 1984, 139, 333.
121. A.G. Thomas, W.R. Flavell, A.K. Mallick, A.R. Kumarasinghe, D.Tsoutsou, N. Khan, C. Chatwin, S. Rayner and G.C. Smith, Phys.
Rev. B, 2007, 75, 035105.
122. X. Wang, J.G. Li, H. Kamiyama, M. Katada, N. Ohashi, Y.
Moriyoshi and T. Ishigaki, J. Am. Chem. Soc, 2005, 127, 10982.
123. D. Vogtender, R. Poducky, J. Redinger, E.L.D. Habenstreit, W.
Habenstreit and U. Diebold, Phys. Rev. B, 2002, 65, 125411.
124. M. Durr, S. Rosselli, A. Yasuda and G. Nelles, J. Phys. Chem. B, 2006, 110, 21899.
125. C. Kim, K.S. Kim, H.Y. Kim and Y.S. Han, J. Mater. Chem, 2008, 18, 5809.
126. I. Robel, M. Kuno and P.V. Kamat, J. Am. Chem. Soc, 2007, 129, 4136.
127. M. Adachi, M. Sakamoto, J. Jiu, Y. Ogata and S. Isoda, J. Phys.
Chem. B, 2006, 110, 13872.
128. W. Yu, L. Qu, W. Guo and X. Peng, Chem. Mater, 2003, 15, 285.