臺灣博碩士論文加值系統

再生能源的需求增加，染料敏化太陽能電池具有多樣性及低的製造成本，因而被廣泛的研究其光電上的應用。染料敏化太陽能電池中，光敏染料是其中一個重要元件，其吸收太陽光輻射，並將其轉換為電能。至今，染料敏化太陽能電池的文獻中大部分多是以具有雙吡啶環和多吡啶環的含釕金屬染料為主。但釕金屬在地球上的含量並不豐富，因此增加了其製造的成本。於是我們設計了一種新的類型的有機染料能與其他的金屬行成錯合物，例如鈷、鎳、銅、鋅、鈀、鉑。希望這一系列含非釕金屬錯合物具有不錯的光電轉換效率。

With increasing renewable energy demands, dye-sensitized solar cells (DSSCs) are being explored extensively for photovoltaic applications because of their versatility and low cost of manufacture. In these cells the sensitizer is one of the key components, harvesting the solar radiation and converting it to electric current. To date, the only ruthenium sensitizers for DSSC applications that have been described in the literature are those bearing bipyridine or polypyridine ligands. But ruthenium metal is not full in the earth，therefore enhances the cost of manufacture. We design the new class of organic dye with different metal like Co, Ni, Cu, Zn, Pd, Pt were used complex with compound as sensitizer. We hope the kind of Metal salen-ligand complexes could get good performance in DSSCs.

總目錄
摘要 I
ABSTRACT II
誌謝 III
總目錄 IV
圖目錄 VI
表目錄 VII
第一章 緒論 1
1-1 前言 1
1-2 太陽能電池的發展與種類 2
1-2-1　矽基型太陽能電池 3
1-2-2　無機化合物半導體型太陽能電池 3
1-2-3　有機化合物薄膜太陽能電池 4
1-3　　染料敏化太陽能電池 5
1-3-1　基本構造及工作原理 6
1-3-2　光敏化染料 11
1-3-2-1 有機金屬錯合物 12
1-3-2-2 有機染料 20
1-3-3　半導體電極 25
1-3-4 電解液 26
第二章 結果與討論 29
2-1 結構設計概念與動機 29
2-2 合成策略 32
2-2-1　Lithium-halogen exchange 34
2-2-2　Stille coupling（1） 36
2-2-3　Suzuki coupling 37
2-2-4　Knoevenagel condensations reaction 38
2-2-5　Schiff bases(1) 40
2-2-6　Synthesis phosphonium salts 43
2-2-7　Wittig reaction 44
2-2-8　palladium catalysed tin-for-bromo exchange reaction 47
2-2-9 Stille coupling（2） 48
2-2-10 Deprotection and reduction reaction 48
2-2-11 schiff bases 49
2-3 未來展望 50
第三章 實驗部分與光譜數據 51
3-1　　實驗儀器 51
3-2　　實驗藥品 52
3-3　　實驗步驟與光譜數 53
參考文獻 65
附圖 69

[1] Chapin, D. M.; Fuller, C. S.; Pearson, G. L. J. Appl.
Phys. 1954, 25 , 676.
[2] Green, M. A.; Emery, D. L.; King, et al. Pro.
Photovoltaics. 2007,15, 35.
[3] Grätzel, M. Nature, 2001, 414, 338.
[4] Hurd, F. ; Livingeston, R. J. Phys. Chem. 1940, 44,
865.
[5] Oster, G.; Bellin, J. S.; Kimball, R. W.; Schrader, M.
E. J. Am. Chem. Soc. 1959, 81, 5095.
[6] Chaberek, S. ; Shepp, A. ; Allen, ,R. J. J. Phys.
Chem. 1965, 69, 641.
[7] Chaberek, S. ; Shepp, A. ; Allen, ,R. J. J. Phys.
Chem. 1965, 69, 647.
[8] Chaberek, S. ; Shepp, A. ; Allen, ,R. J. J. Phys.
Chem. 1965, 69, 2834.
[9] Chaberek, S. ; Shepp, A. ; Allen, ,R. J. J. Phys.
Chem. 1965, 69, 2842.
[10] Kearns, D. R.; Hollins, R. A.; Khan, A. U.; Chambers,
R. W.; Radlick, P. J. Am. Chem. Soc. 1967, 89, 5455.
[11] Kearns, D. R.; Hollins, R. A.; Khan, A. U.; Chambers,
R. W.; Radlick, P. J. Am. Chem. Soc. 1967, 89, 5456.
[12] Tsubomura, H.; Matsumura, M.; Nomura, Y.; Amamiya, T.
Nature 1976, 261, 402.
[13] O’Regan, B.; Grätzel, M. Nature, 1991, 353, 737.
[14] Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humpbry, B.
R.; Miiller, E.; Liska, P.; Vlachopoulos, N.;
Grätzel, M. J. Am. Chem. Soc. 1993, 115, 6382.
[15] Durrant, J. R.; Haque, S. A. Nature, 2003, 2, 362.
[16] Vlachopoulos, N.; Liska, P.; Augustynski, J.;
Grätzel, M. J. Am. Chem. Soc. 1988, 110, 1216.
[17] Grätzel, M. Inorg. Chem. 2005, 44, 6841.
[18] Nazeeruddin, M. K.; Zakeeruddin, S. M.; Humphry-
Baker, R.; Jirousek, M.; Liska, P.; Vlachopoulos, N.;
Shklover, V.; Fischer, C. H.; Grätzel, M. Inorg.
Chem. 1999, 38, 6298.
[19] Nazeeruddin, M. K.; Péchy, P.; Renouard, T.;
Zakeeruddin, S. M.;Humphry-Baker, R.; Comte, P. ;
Liska, P. ; Cevey, L.; Costa, E.; Shklover, V.;
Spiccia, L.; Deacon, G. B.; Bignozzi, C. A.; Grätzel,
M. J. Am. Chem. Soc. 2001, 123, 1613.
[20] Wang, P.; Zakeeruddin, S. M.; Moser, J. E.;
Nazeeruddin, M. K.; Sekiguchi, T.; Grätzel, M. Nat.
Mater. 2003, 2, 42.
[21] Wang, P.; Klein, C.; Moser, J. E.; Humphry-Baker, R.;
Cevey-Ha, N. L.; Carvet, R.; Comte, P.; Zakeeruddin,
S. M.; Grätzel, M. J. Phys. Chem. B 2004, 108, 17553.
[22] Hirata, N.; Lagref, J. J.; Palomares, E. J.; Durrant,
J. R.;Nazeeruddin, M. K.; Grätzel, M.; Censo, D. D.
Chem. Eur. J. 2004,
10, 595.
[23] Wang, P.; Klein, C.; Zakeeruddin, S. M.; Moser, J.
E.; Humphry-Baker, R.; Comte, P.; Aranyos,
V.;Hagfeldt, A.;Nazeeruddin, M. K.; Grätzel, M. Adv.
Mater. 2004, 16, 1806.
[24] Wang, P.; Klein, C.; Humphry-Baker, R.; Zakeeruddin,
S. M.;Grätzel, M. J. Am. Chem. Soc. 2005, 127, 808.
[25] Nazeeruddin, M. K.; Wang, Q.; Cevey, L.; Aranyos, V.;
Liska, P.;Figgemeier, E.; Klein, C.; Hirata, N.;
Koops, S.; Haque, S. A.; Durrant, J. R.; Hagfeldt,
A.; Lever, A. B. P.;Grätzel, M. Inorg. Chem. 2006,
45, 787.
[26] Kuang, D.; Klein, C.; Ito, S.; Moser, J. E.; Humphry-
Baker, R.; Zakeeruddin, S. M.; Grätzel, M. Adv.
Funct. Mater. 2007, 17, 154.
[27] Kuang, D.; Klein, C.; Ito, S.; Moser, J. E.; Humphry-
Baker, R.; Evans, N.; Duriaux, F.; Grätzel, C.;
Zakeeruddin, S. M.; Grätzel, M.Adv. Mater. 2007, 19,
1133.
[28] Jiang, K. J.; Masaki, N.; Xia, J. B.; Noda, S.;
Yanagida, S. Chem.Commun. 2006, 2460.
[29] Chen, C. Y; Wu, S. J.; Wu, C. G.; Chen, J. G.; Ho, K.
C. Angew.Chem. Int. Ed. 2006, 45, 5822.
[30] Chen, C. Y; Chen, J. G.; Wu, S. J.; Li, J. Y.; Wu, C.
G.; Ho, K. C.Angew. Chem. Int. Ed. 2008, 47, 7342.
[31] Chen, C. Y; Wu, S. J.; Li, J. Y.; Wu, C. G.; Chen, J.
G.; Ho, K. C.Adv. Mater. 2007, 19, 3888.
[32] Beaaho, T.; Yoneda, E.; Yum, J. H.; Guglielmi, M.;
Tavernelli, I.;Imai, H.; Rothlisberger, U.;
Nazeeruddin, M. K.; Grätzel, M. J. Am.Chem. Soc.
2009, 131, 5930.
[33] Mishra, A.; Fischer, M. K. R.; Bäuerle, P. Angew.
Chem. Int. Ed.2009, 48, 2474.
[34] Hara, K.; Kurashige, M.; Ito, S.; Shinpo, A.; Suga,
S.; Sayama, K.;Arakawa, H. Chem. Commun. 2003, 252.
[35] Hara, K.; Sato, T.; Katoh, R.; Furube, A.; Yoshihara,
T.; Murai, M.;Kurashige, M.; Ito, S.; Shinpo, A.;
Suga, S.; Arakawa, H. Adv.Funct. Mater. 2005, 15, 246.
[36] Hara, K.; Sayama, K.; Ohga, Y.; Shinpo, A.; Suga, S.;
Arakawa, H.Chem. Commun. 2004, 16, 1806.
[37] Hara, K.; Kurashige, M.; Dan-no, Y.; Kasada, C.;
Shinpo, A.; Suga,S.; Sayama, K.; Arakawa, H. New. J.
Chem. 2003, 27, 783.
[38] Wang, Z. S.; Cui, Y.; Dan-no, Y.; Kasada, C.; Shinpo,
A.; Hara, K.;J. Phys. Chem. 2007, 111, 7224.
[39] Wang, Z. S.; Koumura, N.; Cui, Y.; Takahashi, M.;
Sekiguchi, H.; Mori, A.; Kubo, T.; Furube, A.; Hara,
K. Chem. Mater. 2008, 20,3993.
[40] Choi, H.; Baik, C.; Kang, S. O.; Ko, J.; Kang, M. S.;
Nazeeruddin,M. K.; Grätzel, M. Angew. Chem. 2008,
120, 333 ; Angew. Chem.Int. Ed. 2008, 47, 327.
[41] Hwang, S.; Lee, J. H.; Park, C.; Lee, H.; Kim, C.;
Lee, M. H.; Lee,W.; Park, J.; Kim, K.; Park, N. G.;
Kim, C. Chem. Commun. 2007,4887.
[42] Schemidt-Mende, L.; Bach, U.; Humphry-Baker, R.;
Horiuchi, T.;Miura, H.; Ito, S.; Uchida, S.; Grätzel,
M. Adv. Mater. 2005, 17,813.
[43] Horiuchi, T.; Miura, H.; Sumioka, K.; Uchida, S. J.
Am.Chem. Soc.2004, 126, 12218.
[44] Ito, S.; Miura, H.; Uchida, S.; Takata, M.; Sumioka,
K.; Liska, P.;Comte, P.; Pechy, P.; Grätzel, M. Chem.
Commun. 2008, 5194.
[45] Ooyama, Y.; Harima, Y. Eur. J. Org. Chem. 2009, 2903.
[46] Kunkely, H.; Vogler, A. Inorganica Chimica Acta. 2001, 321,171..
[47] Kleij, A. W.; Kuil, M.; Tooke, D. M.; Lutz, M.; Spek,
A. L.; Reek,J.N.H. Chem. Eur. J. 2005, 11, 4743.
[48] Kalyanasundaram, K.; Vlachopoulos, N.; Krishnan, V.;
Monnier, A.;Grätzel, M. J. Phy. Chem. 1987, 91, 2342.
[49] Wang, Q.; Campbell, W. M.; Bonfantani, E. E.; Jolley,
K. W.;Officer, D. L.; Walsh, P. J.; Gordon, K.;
Humphry-Baker, R.; Nazeeruddin, M. K.; Grätzel, M. J.
Phy. Chem. B 2005, 109, 15397.