臺灣博碩士論文加值系統

本論文利用Stille coupling、Buchwald-Hartwig coupling與Knoevenagel condensation等反應，合成出一系列非金屬系有機光敏染料（metal-free organic dyes）。此系列染料以arylamine作為電子予體（donor），2-cyanoacrylic acid為電子受體（acceptor），並以噻吩香稠環(thieno[3,4-b]thiophene)為共軛架橋（spacer）並引入呋喃（furan）、噻吩（thiophene）等芳香雜環所組成。
此系列染料藉由引入低能帶片段以利吸收波長（λabs）座落在較長的波段，這些化合物之電荷轉移吸收的確出現於477−553 nm之間。經電化學與吸收光譜量測推算出此系列染料之HOMO與LUMO能階範圍分別約在5.23−5.48與3.14−3.37 eV之間，因此染料皆可以順利將電子注入TiO2光導電極以及隨後藉由電解質還原而。以這些染料組裝成的染料敏化太陽能電池（dye-sensitized solar cells, DSSCs）的光電轉換效率為1.23−5.31%。在相同條件下和N719染料製成的標準元件比較，可達標準元件效率的17−72%。

A novel series of metal-free organic dyes were synthesized via Stille coupling, Buchwald-Hartwig coupling and Knoevenagel condensation. These dyes are composed of an arylamine moiety as the electron donor, a conjugated spacer containing ethyl thieno[3,4-b]thiophene-2-carboxylate, and furan (or thiophene) as the electron transmitting bridge, and an 2-cyanoacrylic acid as the electron acceptor and anchoring group to the TiO2 surface.
The lowbandgap thieno[3,4-b]thiophene entity was incorporated in the conjugated spacer of the sensitizer for red shifting the absorption band. Indeed, the charge-transfer absorption maximum of the sensitizer ranges from 477 to 553 nm. Cyclic voltammograms and absorption spectra were used to calculate the HOMO and LUMO energy levels of these dyes, The HOMO and LUMO energies fall in the range of 5.23−5.48 and 3.14−3.37 eV, respectively, which facilitate both electron injection to TiO2 and subsequent dye regeneration. Dye-sensitized solar cells (DSSCs) using these dyes exhibit high solar energy-to-electricity conversion efficiencies ranging from 1.23% to 5.31%, which reach 17−72% of the standard device of N719 fabricated and measured under the same conditions.

中文摘要 -------------------------------------------------- I
英文摘要 ------------------------------------------------- II
謝誌 --------------------------------------------------- III
目錄 ----------------------------------------------------- V
圖目錄 -------------------------------------------------- VII
表目錄 -------------------------------------------------- XI
附圖目錄 ------------------------------------------------ XII
第一章 緒論 ----------------------------------------------- 1
1-1 前言 ------------------------------------------------- 1
1-2 太陽能量光譜介紹 --------------------------------------- 2
1-3 太陽能電池簡介 ----------------------------------------- 4
第二章 染料敏化太陽能電池介紹與研究理論說明 -------------------- 13
2-1 染料敏化太陽能電池的基本結構 ------------------------- 13
2-2 染料敏化太陽能電池機制與原理 ------------------------- 30
2-3 太陽能電池電壓-電流輸出參數及特性說明 ------------ 35
2-4 研究動機 --------------------------------------------- 37
第三章 實驗部分和過程說明 ----------------------------------- 41
3-1 實驗儀器之原理與操作 ----------------------------------- 41
3-2 實驗藥品及溶劑 ---------------------------------------- 45
3-3 合成系列染料流程與步驟 ---------------------------------- 47
第四章 結果與討論 ----------------------------------------- 80
4-1 合成及實驗反應機構之探討 ------------------------------- 80
4-2 有機染料光物理性質之探討 ------------------------------- 86
4-3 電化學性質之探討 ------------------------------------- 90
4-4 元件製作與效率 --------------------------------------- 93
4-5理論計算 -------------------------------------------- 100
4-6 結論與展望 ------------------------------------------ 111
參考文獻 ------------------------------------------------ 112
附圖 --------------------------------------------------- 122

1.張正華, 李陵嵐, 葉楚平, 楊平華, 馬振基, 有機與塑膠太陽能電池.五南, 2007, 1.
2.H. Kallmans, M. Pope, J. Chem. Phys. 1958, 30, 585.
3.D. M. Chapin, C. S. Fuller, G. L. Pearson, J. Appl. Phys. 1954, 25, 676.
4.S.Y. Dai, K.J. Wang, Q C. Wu, Y. Wang, Acta. Energiae Solaris Sinica 1997, 18, 228.
5.H. Kallmans, M. Pope, J. Chem. Phys. 1958, 30, 585.
6.黄建昇, 結晶矽太陽能電池發展近況. 工業材料雜誌 2003, 150.
7.郭明村, 薄膜太陽能電池發展近況. 工業材料雜誌 2003, 138.
8.S. Guha et al, Appl. Phys. Lett. 1999, 74, 1860.
9.H. Shirakawa, C. K. Chiang, C. R. Fincher, Y. W. Park, A. J. Heeger, E. J. Louis, S. C. Gau, A. G. MacDiarmid, Phys. Rev. Lett. 1977, 39, 1098.
10.L. Bozano, S. A. Carter, J. C. Scott, G. G. Malliaras, P. J. Brock, Appl. Phys. Lett. 1999, 74, 1132.
11.X. Peng, M. C. Schlamp, A. Kadavanich, A. P. Alivisatos, J. Am. Chem. Soc. 1997, 119, 7019.
12.S. E. Shaheen, C. J. Brabec, N. S. Sariciftci, F. Padinger, T. Fromherz, J. C. Hummelen, Appl. Phys. Lett. 2001, 78, 841.
13.M. Berggren, O. Inganäs, G. Gustafsson, J. C. Carberg, J. Rasmusson, M. R. Anderson, T. Hjertberg, O. Wennerstron, Nature 1994, 372, 444.
14.S. Chaberek, A. Sheep, R. J. Allen, J. Am. Chem. Soc. 1967, 89, 5456.
15.H. Tsubomura, M. Matsumura, Y. Nomura, T. Amamiya, Nature 1976, 261, 402.
16.B. O. Regan, M. Grätzel, Nature. 1991, 353, 737.
17.(a) M. Grätzel, Inorg. Chem. 2005, 44, 6841. (b) P. Wang, M. Gratzel, J. Phys. Chem. C. 2009, 113, 6290. (c) C.-G. Wu, M. Gratzel, ACS Nano, 2009, 3, 3103.
18.A. B. F. Martinson, T. W. Hamann, M. J. Pellin, J. T. Hupp, Chem. Eur. J. 2008, 14, 4458.
19.http://www.anl.gov.
20.A. Vittadini, A. Selloni, F. P. Rotzinger, and M. Grätzel, J. Phys. Chem. B 2000, 104, 1300.
21.A. Vittadini, A. Selloni, F. P.Rotzinger, M. Grätzel, J. Phys. Chem. B 2000, 104, 1300.
22.(a) S. H. Kang, S.-H. Choi, M.-S. Kang, J.-Y. Kim, H.-S. Kim, T. Hyeon, Y.-E. Sung, Adv. Mater. 2008, 20, 54. (b) A. Ghicov, S. P. Albu, R. Hahn, D. Kim, T. Stergiopoulos, J. Kunze, C.-A. Schiller, P. Falaras, P. Schmuki, Chem. Asian J. 2009, 4, 520. (c) Y. Kim, C.-H. Kim, Y. Lee, K.-J. Kim, Chem. Mater. 2010, 22, 207. (d) J.-K. Oh, J.-K. Lee, H.-S. Kim, S.-B. Han, K.-W. Park, Chem. Mater. 2010, 22, 1114.
23.J. Xia, N. Masaki, K. Jiang, S. Yanagida, J. Phys. Chem. C 2007, 111, 8092.
24.K. Tennakone, G. R. R. A. Kumara, A. R. Kumarasinghe, K. G. U. Wijayantha, P. M. Sirimanne, Semicond. Sci. Technol. 1995, 10, 1689.
25.Y. Gil, Y. Tsur, O. M. Umurhanand, I. Riess, J. Phys. D: Appl. Phys. 2008, 41, 135106.
26.D. P. Hagberg, T. Edvinsson, T. Marinado, G. Boschloo, A. Hagfeldt, L. Sun, Chem. Commun. 2006, 2245.
27.S.-L. Li, K.-J. Jiang, K.-F. Shao, L.-M. Yang, Chem. Commun. 2006, 2792.
28.N. Koumura, Z.-S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc. 2006, 128, 14256.
29.S. Kim, J. K. Lee, S. O. Kang, J. Ko, J.-H. Yum, S. Fantacci, D. De Angelis, D. D. Censo, M. K. Nazeeruddin, M. Grätzel, J. Am. Chem. Soc. 2006, 128, 16701.
30.P. Qin, X. Yang, R. Chen, L. Sun, T. Marinado, T. Edvinsson, G. Boschloo, A. Hagfeldt, J. Phys. Chem. C 2007, 111, 1853.
31.M. K. Nazeeruddin, A. Kay, L. Rodicio, R. Humphry-Baker, E. Müller, P. Liska, N. Vlachopoulos, M. Grätzel, J. Am. Chem. Soc. 1993, 115, 6382.
32.M. K. Nazeeruddin, R. Humphry-Baker, P. Liska, M. Grätzel, J. Phys. Chem. B 2003, 107, 8981.
33.M. K. Nazeeruddin, P. Péchy, T. Renouard, M. S. Zakerruddin, R. Humphry-Baker, P. Comte, P. Liska, Le Cevey, E. Costa, V. Shklover, L. Spiccia, G. B. Deacon, C. A. Bignozzi, M. Grätzel, J. Am. Chem. Soc. 2001, 123, 1613.
34.K. Finnie, J. Bartiett, J. Woolfrey, Langmuir 1998, 14, 2744.
35.K. Sayama, H. Sugihara, H. Arakawa, Chem. Mater. 1998, 10, 3825.
36.W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan, and P. Wang, Chem. Mater. 2010, 22, 1915.
37.(a) K. Hara, K. Miyamoto, Y. Abe, M. Yanagida, J. Phys. Chem. B 2005, 109, 23776. (b) K. Hara, T. Sato, R. Katoh, A. Furube, Y. Ohga, A. Shinpo, S. Suga, K. Sayama, H. Sugihara, H. Arakawa, J. Phys. Chem. B 2003, 107, 597. (c) Z. Wang, Y. Cui, K. Hara, Y. Dan-oh, C. Kasada, A. Shinpo, Adv. Mater. 2007, 19, 1138. (d) Z. Wang, Y. Cui, Y. Dan-oh, C. Kasada, A. Shinpo, K. Hara, J. Phys. Chem. C 2007, 111, 7224.
38.(a) T. Horiuchi, H. Miura, K. Sumioka, S. Uchida, J. Am. Chem. Soc. 2004, 126, 12218. (b) L. Schmidt-Mende, U. Bach, R. Humphry-Baker, T. Horiuchi, H. Miura, S. Ito, S. Uchida, M. Grätzel, Adv. Mater. 2005, 17, 813. (c) D. Kuang, S. Uchida, R. Humphry-Baker, S. M. Zakeeruddin, M. Grätzel, Angew. Chem. Int. Ed. 2008, 47, 1923.
39.(a) T. Kitamura, M. Ikeda, K. Shigaki, T. Inoue, N. A. Anderson, X. Ai, T. Lian, S. Yanagida, Chem. Mater. 2004, 16, 1806. (b) K. Hara, T. Sato, R. Katoh, A. Furube, T. Yashihara, M. Murai, M. Kurashige, S. Ito, A. Shinpo, S. Suga, H. Arakawa, Adv. Funct. Mater. 2005, 15, 246.
40.(a) Q.-H. Yao, F.-S. Meng, F.-Y. Li, H. Tian, C.-H. Huang, J. Mater. Chem. 2003, 13, 1048. (b) Q.-H. Yao, L. Shan, F.-Y. Li, D.-D. Yin, C.-H. Huang, New J. Chem. 2003, 27, 1277. (c) Y. Chen, C. Li, Z. Zeng, W. Wang, X. Wang, B. Zhang, J. Mater. Chem. 2005, 15, 1654.
41.(a) X. Ma, J. Hua, Y. Jin, F. Meng, W. Zhan, H. Tian, Tetrahedron 2008, 64, 345. (b) W. Zhan, W. Wu, J. Hua, Y. Jing, F. Meng, H. Tian, Tetrahedron Lett. 2007, 48, 2461.
42.(a) S. Ferrere, A. Zaban, B. A. Gregg, J. Phys. Chem. B, 1997, 101, 4490. (b) T. Edvinsson, C. Li, N. Pschirer, J. Schoneboom, F. Eickemeyer, R. Sens, G. Boschloo, A. Herrmann, K. Mullen, A. Hagfeldt, J. Phys. Chem. C 2007, 111, 15137. (c) Y. Shibano, T. Umeyama, Y. Matano, H. Imahori, Org. Lett. 2007, 9, 1971. (d) S. Ferrere, B. A. Gregg, New J. Chem. 2002, 26, 1155.
43.K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara, H. Arakawa, Chem. Lett. 2000, 29, 316.
44.(a) J. R. Mann, M. K. Gannon, T. C. Fitzgibbons, M. R. Detty, D. F. Watson, J. Phys. Chem. C 2008, 112, 13057. (b) G. Zhou, N. Pschirer, J. C. Schoneboom, F. Eickemeyer, M. Baum-garten, K. Mullen, Chem. Mater. 2008, 20, 1808. (c) K. Sayama, M. Sugino, H. Sugihara, Y. Abe, H. Arakawa, Chem.Lett. 1998, 753. (d) K. Hara,T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara, H. Arakawa, Sol. Energy Mater. Sol. Cells 2000, 64, 115.
45.(a) K. R. Justin Thomas, J. T. Lin, Y.-C. Hsu, K.-C. Ho, Chem. Commun. 2005, 4098. (b) K. Hara, Z.-S. Wang, T. Sato, A. Furube, R. Katoh, H. Sugihara, Y. Dan-oh, C. Kasada, A. Shinpo, S. Suga, J. Phys. Chem. B 2005, 109, 15476. (c) S. Tan, J. Zhai, H. Fang, T. Jiu, J. Ge, Y. Li, L. Jiang, D. Zhu, Chem. Eur. J. 2005, 11, 6272. (d) S.-L. Li, K.-J. Jiang, K.-F. Shao, L.-M. Yang, Chem. Commun. 2006, 2792. (e) N. Koumura, Z.-S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc. 2006, 128, 14256. (f) S. Kim, J. K. Lee, S. O. Kang, J. Ko, J.-H. Yum, S. Fantacci, F. De Angelis, D. D. Censo, M. K. Nazeeruddin, M. Grätzel, J. Am. Chem. Soc. 2006, 128, 16701. (g) C.-Y. Chen, S.-J. Wu, C.-G. Wu, J.-G. Chen, K.-C. Ho, Angew. Chem. Int. Ed. 2006, 45, 1. (h) H. Choi, J. K. Lee, K. H. Song, K. Song, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 1553. (i) D. Kim, J. K. Lee, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 1913. (j) H. Choi, J. K. Lee, K. Song, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 3115. (k) R. Chen, X. Yang, H. Tian, L. Sun, J. Photochem. Photobiol. A 2007, 189, 295. (l) S. Kim, H. Choi, D. Kim, K. Song, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 9206.
46.(a) S. Hwang, J. H. Lee, C. Park, H. Lee, C. Kim, C. Park, M. H. Lee, W. Lee, J. Park, K. Kim, N. G. Park, C. Kim, Chem. Commun. 2007, 46, 4887. (b) D. P. Hagberg, T. Marinado, K. M. Karlsson, K. Nonomura, P. Qin, G. Boschloo, T. Brinck, A. Hagfeldt, L. Sun, J. Org. Chem. 2007, 72, 9550. (c) M. Velusamy, K. R. JustinThomas, J. T. Lin, Y. C. Hsu, K. C. Ho, Org. Lett. 2005, 7, 1899. (d) M. Liang, W. Xu, F. Cai, P. Chen, B. Peng, J. Chen, Z. Li, J. Phys.Chem. C 2007, 111, 4465. (e) W. Xu, B. Peng, J. Chen, M. Liang, F. Cai, J. Phys. Chem. C 2008, 112, 874. (f) M. S. Tsai, Y. C. Hsu, J. T. Lin, H. C. Chen, C. P. Hsu, J. Phys. Chem. C 2007, 111, 18785. (g) T. Kitamura, M. Ikeda, K. Shigaki, T. Inoue, N. A. Anderson, X. Ai, T. Lian, S. Yanagida, Chem. Mater. 2004, 16, 1806. (h) Z. Ning, Q. Zhang, W. Wu, H. Pei, B. Liu, H. Tian, J. Org. Chem. 2008, 73, 3791.
47.(a) S. L. Li, K. J. Jiang, K. F. Shao, L. M. Yang, Chem. Commun. 2006, 26, 2792. (b) K. Hara, T. Sato, R. Katoh, A. Furube, T. Yoshihara, M. Murai, M. Kurashige, S. Ito, A. Shinpo, S. Suga, H. Arakawa, Adv. Funct. Mater. 2005, 15, 246. (c) T. Kitamura, M. Ikeda, K. Shigaki, T. Inoue, N. A. Anderson, X. Ai, T. Q. Lian, S. Yanagida, Chem. Mater. 2004, 16, 1806. (d) K. Hara, M. Kurashige, S. Ito, A. Shinpo, S. Suga, K. Sayama, H. Arakawa, Chem. Commun. 2003, 252.
48.(a) S. Erten-Ela, M. D. Yilmaz, B. Icli, Y. Dede, S. Icli, E. U. Akkaya, Org. Lett. 2008, 10, 3299. (b) D. Kumaresan, R. Thummel, T. Bura, G. Ulrich, R. Ziessel, Chem. Eur. J. 2009, 15, 6335.
49.(a) R. Chen, X. Yang, H. Tian, X. Wang, A. Hagfeldt, L. Sun, Chem. Mater. 2007, 19, 4007. (b) R. Chen, X. Yang, H. Tian, L. Sun, J. Photochem. Photobiol. A 2007, 189, 295.
50.(a) N. Koumura, Z. S. Wang, S. Mori, M. Miyashita, E. Suzuki, K. Hara, J. Am. Chem. Soc. 2006, 128, 14256. (b) D. Kim, J. K. Lee, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 1913. (c) Z.-S. Wang, N. Koumura, Y. Cui, M. Takahashi, H. Sekiguchi, A. Mori, T. Kubo, A. Furube, K. Hara, Chem. Mater. 2008, 20, 3993.
51.(a) P. Qin, X. Yang, R. Chen, L. Sun, T. Marinado, T. Edvinsson, G. Boschloo, A. Hagfeldt, J. Phys. Chem. C 2007, 111, 1853. (b) R. Chen, X. Yang, H. Tian, L. Sun, J. Photochem. Photobiol. A 2007, 189, 295. (c) S. Kim, H. Choi, D. Kim, K. Song, S. O. Kang, J. Ko, Tetrahedron 2007, 63, 9206.
52.Daniel P. H., Tannia M., Karl M. K., Kazuteru N., Peng Q., Gerrit B., Tore B., Anders H., and Licheng S., J. Org. Chem. 2007, 72, 9550.
53.(a) A. K.-Y. Jen, V. P. Rao, K. Y. Wong, K. J. Drost, J. Chem. Soc., Chem. Commun. 1993, 90. (b) V. P. Rao, A. K.-Y. Jen, K. Y. Wong, K. J. Drost, J. Chem. Soc., Chem. Commun. 1993, 1118. (c) V. P. Rao, Y. M. Cai, A. K.-Y. Jen, J. Chem. Soc., Chem. Commun. 1994, 1689. (d) P. R. Varanasi, A. K.-Y. Jen, J. Chandrasekhar, I. N. N. Namboothiri, A. Rathna, J. Am. Chem. Soc., 1996, 118, 12443. (e) A. K.-Y. Jen, Y. Cai, P. V. Bedworth, S. R. Marder, Adv. Mater. 1997, 9, 132. (f) S.-S. P. Chou, C.-H. Shen, Tetrahedron Lett. 1997, 38, 6407. (g) I. D. L. Albert, T. J. Marks, M. A. Ratner, J. Am. Chem. Soc. 1997, 119, 6575.
54.Y.-S. Yen, Y.-C. Hsu, J. T. Lin, C.-W. Chang, C.-P. Hsu, D.-J. Yin, J. Phys. Chem. C. 2008, 112, 12557.
55.J. T. Lin P.-C. Chen, Y.-S. Yen, Y.-C. Hsu, H.-H. Chou, M.-C. P. Yeh,
Org. Lett. 2009, 11, 97.
56.C.-H. Chen, Y.-C. Hsu, H.-H. Chou, K. R. Justin Thomas, J. T. Lin, and C.-P. Hsu, Chem. Eur. J. 2010, 16, 3184.
57.(a) R. Yang, R. Tian, Q. Hou, W. Yang, Y. Cao, Marcomolecules 2003, 36, 7453. (b) A. R. Katritzky, A. F. Pozharskii, Handbook of Heterocyclic Chemistry, 2nd ed. Pergamon: Oxford 2000, Chapter 2, pp 79-82.
58.J.-J. Kim, H. Choi, M.-S. Lee, M.-S. Kang, K. Song, S. O. Kang, J. Ko, J. Mater. Chem. 2008, 18, 5223.
59.A. Hagfeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev. 2010, 110, 6595.
60.J. Ferber, R. Stangl, J. Luther, Solar Energy Mater. Solar Cells 1998, 53, 29.
61.A. B. F. Martinson, T. W. Hamann, M. J. Pellin, and J. T. Hupp, Chem. Eur. J. 2008, 14, 4458.
62.D. W. Hawkins, B. Iddon, S. Darren, S. Longthorneb, P. J. Rosyk, J. Chem. Soc. Perkin Trans. 1 1994, 2735.
63.S. Y. Hong and D. S. Marynick, Macromolecules 1992, 25, 4652.
64.Y.-J. Cheng, S.-H. Yang, and C.-S. Hsu, Chem. Rev. 2009, 109, 5868.
65.C. J. Neef, I. D. Brotherston, J. P. Ferraris, Chem. Mater. 1999, 11, 1957.
66.(a)K. Lee, G. A. Sotzing, Macromolecules 2001, 34, 5746. (b) G. A. Sotzing, K. Lee, Macromolecules 2002, 35, 7281.
67.M. Pomerantz, X. Gu, S. X.g Zhang, Macromolecules 2001, 34, 1817
68.B. Y. Yao, Y. Liang, V. Shrotriya, S. Xiao, L. Yu, Y. Yang, Adv. Mater. 2007, 19, 3979.
69.(a) Y. Liang, Y. Wu, D. Feng, S.-T. Tsai, H.-J. Son, G. Li, L. Yu, J. Am Chem. Soc., 2009, 131, 56. (b) Y. Liang, D. Feng, Y. Wu, S.-T. Tsai, G. Li, C. Ray, J. Am. Chem. Soc. 2009, 131, 7792.
70.D. Milstein and J. K. Stille, J. Am. Chem. Soc. 1978, 100, 3636.
71.F. Paul, J. Patt, and J. F. Hartwig, J. Am. Chem. Soc. 1994, 116, 5969.
72.E. Knoevenagel, Chem. Ber. 1898, 31, 2596.
73.Y. J. Su, J. T. Lin, Y.-J. Tao, C.-W. Ko, S.-C. Lin, S. S. Sun, Chem. Mater. 2002, 4, 1884.
74.A. Hagfeldt, M. Grätzel, Acc. Chem. Res. 2000, 33, 269.
75.R. C. Hiborn, Am. J. Phys. 1982, 50, 982.
76.S.-T. Huang, Y.-C. Hsu, Y.-S. Yen, H. S. Chou, J. T. Lin C.-W. Chang, C.-P. Hsu, C. Tasi, D.-J. Yin, J. Phys. Chem. C. 2008, 112, 19739.