利用電子豐盈與電子匱乏芳香環稠合而成之剛硬片段DTBZ (dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-d][1,2,3]triazole)作為雙極性非金屬系有機光敏染料之共軛架橋主體，引入不同的電子予體，如tripheneylamine (TPA)、9-(2-ethylhexyl)-9H-carbazole (CBZ)、4-(2-ethylhexyl)-4H-thieno[3,2-b]indole (TID)，以及不同的共軛架橋延伸片段，如thiophene (T)、3-n-hexyl-thiophene (HT)，並以2-cyanoacrylic acid作為電子受體兼錨基，本研究成功開發出新穎D-A'-A型光敏化染料 (YC系列染料)。本研究也對染料進行了光物理、電化學性質測量，以及製成染料敏化型太陽能電池進行測試，並搭配理論計算探討。
YC系列染料在362 nm到550 nm的光譜範圍有寬廣的吸收，且擁有不錯的消光係數，最高的消光係數達到~54800 M-1 cm-1。由於DTBZ的共面性，染料分子在TiO2上有相當程度的J-型堆疊，使得分子的吸收延伸至較長的波段。在標準AM 1.5光照度下，YC系列元件之光電轉換效率在5.82%到8.51%之間，最佳的YC-5 (8.51%)且超越標準品N719元件(8.12%)。從IPCE光譜可以很清楚看出J-型堆疊對於光電流的增益有很重要的貢獻，若加入5 mM的共吸附劑 (CDCA) 適度抑制堆疊導致的激態分子淬息，但保存長波段的光吸收，可將效率更提升至9.1%，且在1/4個標準太陽光照度下，其效率更可提升至10.56%。

New D-A'-A type sensitizers (YC dyes), comprising different arylamine (tripheneylamine, 9-(2-ethylhexyl)-9H-carbazole or 4-(2-ethylhexyl)-4H-thieno[3,2-b]indole) as the electron donor, dithieno[3',2':3,4;2'',3'':5,6]benzo[1,2-d][1,2,3]triazole (DTBZ) with fused electron rich and electron deficient aromatic units as the rigidified π-conjugated spacer, and 2-cyanoacrylic acid as both the acceptor and anchor, have been synthesized and characterized. Thiophene or 3-n-hexyl-thiophene was also introduced to extend the conjugation. In addition to the investigation of the photophysical, electrochemical properties, theoretical computations were also carried out on these new dyes. Dye-sensitized solar cells were fabricated using these dyes as the senzitizers, and relevant physical measurements were conducted.
The YC sensitizers displayed broad absorption spectra covering the range of 362 to 550 nm, with the highest molar extinction coefficient up to ~54,800 M-1cm-1. Because of the planarity nature of DTBZ, the dyes have J-aggregation when adsorbed on the TiO2 surface, resulting extended absorption in the longer wavelength region. The light-to-electricity conversion efficiencies of the dye-sensitized solar cells (DSSCs) fabricated from the dyes range from 5.82 to 8.51% under simulated AM 1.5 G illumination, and the best cell efficiency (YC-5) surpasses that (8.12%) of the standard DSSC based on N719 ((bis(tetrabutyl-ammonium)-cis-di(thiocyanato)-N,N'-bis(4-
carboxylato-4'-carboxylic acid-2,2'-bipyridine)ruthenium(II)). The IPCE spectra clearly indicates that important contribution of J-aggregation of the dyes to the photocurrents. With addition of 5 mM of CDCA (chenodeoxycholic acid) as the coadsorbent to alleviate excited state quenching while retaining the gain at the longer wavelength region due to dye-aggregation, the best efficinecy was further boosted to 9.10%. Under 25% sunlight illumination, the efficiency reached 10.56%.

1. H. Kallmans; M. Pope, “Photovoltaic effect in organic crystals”, J. Chem. Phys., 1958, 30, 585.
2. M. A. Green; K. Emery; Y. Hishikawa; W. Warta; E. D. Dunlop, “Proceeding of the 21st IEEE Photovoltaic Specialists Conference”, Orlando, USA: IEEE Publication, 1990.
3. D. M. Chapin; C. S. Fuller; G. L. Pearson, “A new silicon p-n junction photocell for converting solar radiation into electrical power”, J. Appl. Phys., 1954, 25, 676.
4. K. Masuko; M. Shigematsu; T. Hashiguchi; D. Fujishima; M. Kai; N. Yoshimura; T. Yamaguchi; Y. Ichihashi; T. Mishima; N. Matsubara; T. T. Yamanishi; T. Takahama; M. Taguchi; E. Maruyama; S. Okamoto, “Achievement of more than 25% conversion efficiency with crystalline silicon heterojunction solar cell”, IEEE J. Photovoltaics, 2014, 4, 1433.
5. W. Deng; D. Chen; Z. Xiong; P. J. Verlinden; J. W. Dong; F. Ye; H. Li; H. J. Zhu; M. Zhong; Y. Yang; Y. F. Chen; Z. Q. Feng, “Altermatt P. 20.8% PERC solar cell on 156 mm x 156 mm p-type nulticrystalline silicon substrate”, IEEE J. Photovoltaics, 2016, 6, 3.
6. T. Matsui; H. Sai; T. Suezaki; M. Matsumoto; K. Saito; I. Yoshida; M. Kondo, “Development of highly stable and efficient amorphous silicon based solar cells”, Proc. 28th European Photovoltaic Solar Energy Conference, 2013.
7. 郭明村, 「薄膜太陽能電池發展近況」, 工業材料雜誌, 2003, 203, 138.
8. National Renewable Energy Laboratory. NREL Best Research Cell Efficiencies Chart; http://www.nrel.gov/ncpv/images/efficiency_ chart.jpg.
9. F. Hurd; R. Livingston,”The Quantum Yields of Some Dye-sensitized Photooxidations”, J. Phys. Chem., 1940, 44, 865.
10. G. Oster; J. S. Bellin; R. W. Kinball; M. E. Scharder, “Dye Sensitized Photoöxidation”, J. Am. Chem. Soc., 1959, 81, 5095.
11. H. Tsubomura; M. Mastsumumuera; Y. Nomura; T. Amamiya, “Dye sensitised zinc oxide: aqueous electrolyte: platinum photocell”, Nature, 1976, 261, 402.
12. B.O. Regan; M. Grätzel, “A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films”, Nature, 1991, 353, 737.
13. M.K. Nazeeruddin; A. Key; I. Rodicio; R. Humphry-Baker; E. Mueller; P. Liska; N. Vlachopoulos; M.Graetzel, “Conversion of light to electricity bycis-X2bis(2,2'-bipyridyl-4,4'-
dicarboxylate) ruthenium(II) charge-transfer sensitizers (X = Cl-, Br-, I-, CN-, and SCN-) on nanocrystalline titanium dioxide electrodes”, J. Am. Chem. Soc., 1993, 115, 6382.
14. M. K. Nazeeruddin; F. D. Angelis; S. Fantacci; A. Selloni; G. Viscardi; P. Liska; S. Ito; B. Takeru and M. Grätzel, “Combined Experimental and DFT-TDDFT Computational Study of Photoelectrochemical Cell Ruthenium Sensitizers”, J .Am. Chem. Soc., 2005, 127, 16835.
15. M. K. Nazeeruddin;P. Péchy; T. Renouard; S. M. Zakeeruddin; R. Humphry-Baker; P. Comte; P. Liska; L. Cevey; E. Costa; V. Shklover; L. Spiccia; G. B. Deacon; C. A. Bignozzi and M. Grätzel, “Engineering of Efficient Panchromatic Sensitizers for Nanocrystalline TiO2-Based Solar Cells”, J. Am. Chem. Soc., 2001, 123, 1613.
16. P. Wang; S. M. Zakeeruddin; J. E. Moser; M. K. Nazeeruddin; T. Sekiguchi and M. Grätzel, “A stable quasi-solid-state dye-sensitized solar cell with an amphiphilic ruthenium sensitizer and polymer gel electrolyte”, Nat. Mater., 2003, 2, 402.
17. F. Gao; Y. Wang; D. Shi;J. Zhang; M.Wang; X. Jing; R. Humphry-Baker; P. Wang; S. M. Zakeeruddin; M. Grätzel, “Enhance the optical absorptivity of nanocrystalline TiO2 film with high molar extinction coefficient ruthenium sensitizers for high performance dye-sensitized solar cells”, J. Am. Chem. Soc., 2008, 130, 10720.
18. C. Y. Chen; M. Wang; J. Y. Li; N. Pootrakulchote; L. Alibabaei; C. Ngoc-le; J. D. Decoppet; J. H. Tsai; C. Grätzel; C. G. Wu; S. M. Zakeeruddin and M. Grätzel, “Highly Efficient Light-Harvesting Ruthenium Sensitizer for Thin-Film Dye-Sensitized Solar Cells”, ACS Nano., 2009, 3, 3103.
19. A. Yella; H. W. Lee; H. N. Tsao; C. Yi; A. K. Chandiran; M. K. Nazeeruddun; E.W. Diau; C. Y. Yeh; S. M. Zakeeruddin; M. Grätzel, “Porphyrin-sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12 percent efficiency”, Science, 2011, 334, 629.
20. S.Mathew; A. Yella; P. Gao; R. Humphry-Baker; B. F. Curchod; N. Ashari-Astani; I. Tavernelli; U. Rothlisberger; M. K. Nazeeruddin; M. Grätzel, “Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers”, Nat.Chem., 2014, 6, 242.
21. Z. Yao; H. Wu; Y. Li; J. Wang;J. Zhang;M. Zhang; Y. Guo and P. Wang, “Dithienopicenocarbazole as the kernel module of low-energy-gap organic dyes for efficient conversion of sunlight to electricity”, Energy Environ. Sci., 2015, 8, 3192.
22. K. Kakiage; Y. Aoyama; T. Yano; K. Oya; J. I. Fujisawab and M. Hanaya, “Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes”, Chem. Commun., 2015, 51, 15894
23. (a) A. R. bin Mohd Yusoff; M. K. Nazeeruddin, “Organic Halide Lead Pervoskites for Photovoltaic Applictions”, J. Phys. Chem. Lett., 2016, 7, 851. (b) H. Snaith, “Pervoskites: the Emergence of a New Era for Low-CostHigh-Efficiency Solar Cells”, J. Phys. Chem. Lett., 2013, 4, 3623.
24. (a) G. H. Carey; A. L. Abdelhady; Z. Ning; S. M. Thon; O. M. Bakr and E. H. Sargent, “Colloidal Quantum Dot Solar Cells”, Chem. Rev., 2015, 115, 12732. (b) W. Li and X. Zhong, “Capping Ligand-Induced Self-Assembly for Quantum Dot Sensitized Solar Cells”, J. Phys. Chem. Lett., 2015, 6, 796. (c) J. Wang, Y. Li, Q. Shen; T. Izuishi; Z. Pan; K. Zhaoa and X. Zhong, “Mn doped quantum dot sensitized solar cells with power conversion efficiency exceeding 9%”, J. Mater. Chem. A, 2016, 4, 877.
25. N. Robertson, “Optimizing dyes for dye-sensitized solar cells”, Angew. Chem. Int. Ed., 2006, 45, 2338.
26. Md. K. Nazeeruddin;R. Humphry-Baker; P. Liska and M. Grätzel, “Investigation of Sensitizer Adsorption and the Influence of Protons on Current and Voltage of a Dye-Sensitized Nanocrystalline TiO2 Solar Cell”, J. Phys. Chem. B, 2003, 107, 8981.
27. W. H. Zhu; Y. Z. Wu; S. Wang; W. Q. Li; X. Li; J. Chem; Z. S. Wang and H. Tian, “Organic D-A-π-A Solar Cell Sensitizers with Improved Stability and Spectral Response”, Adv. Funct. Mater., 2011, 21, 756.
28. M. Velusamy; K. R. Justin Thomas; J. T. Lin; Y. C. Hsu and K. C. Ho, “Organic Dyes Incorporating Low-Band-Gap Chromophores for Dye-Sensitized Solar Cells”, Org. Lett., 2005, 7, 1899.
29. Y. Z. Wu; W. H. Zhu; S. M. Zakeeruddin and M. Grätzel, “Insight into D-A-π-A Structured Sensitizers: A Promising Route to Highly Efficient and Stable Dye-Sensitized Solar Cells”, ACS Appl. Mater. Interfaces, 2015, 7, 9307.
30. H. H. Chou; Y. C. Chen; H. J. Huang; T. H. Lee; J. T. Lin;C.Tsai; K. Chen, “High-performance dye-sensitized solar cells based on 5,6-bis-hexyloxy-benzo[2,1,3]thiadiazole”, J. Mater. Chem., 2012, 22, 10929.
31. Y. S. Yeng; C. T. Lee; C. Y.Hsu; H.-H.Chou; Y. C.Chen; J. T. Lin, “Benzotriazole-Containing D−π−A Conjugated Organic Dyes for Dye-Sensitized Solar Cells”, Chem. Asian J, 2013, 8, 809.
32. J.S. Ni; J.H. You; W.I. Hung; W.S. Kao; H.H. Chou; J.T. Lin, “Organic dyes incorporating the dithieno[3′ ,2′ :3,4;2″ ,3″ :5,6]benzo[1,2-c]furazan moiety for dye-sensitized solar cells”, ACS Appl.Mater. Interfaces, 2014, 6, 22612.
33. J. S. Ni;W. S. Kao; H. J. Chou and J. T. Lin, “Organic Dyes Incorporating the Dithieno[3,2-f:2′,3′-h]quinoxaline Moiety for Dye-Sensitized Solar Cells”,ChemSusChem,2015, 8, 2932.
34. Z. S. Huang; X. F. Zang; T. Hua; L. Y. Wang; H. Meier and D. Cao, “2,3-Dipentyldithieno[3,2‐f:2′,3′‐h]quinoxaline-Based Organic Dyes for Efficient Dye-Sensitized Solar Cells: Effect of π‐Bridges and Electron Donors on Solar Cell Performance”, ACS Appl. Mater. Interfaces, 2015, 7, 20418.
35. Z. S. Huang; H. L. Feng; X. F. Zang; Z. Iqbal; H. Zeng; D. B. Kuang; L. Y. Wang; H. Meierd and D. Cao, “Dithienopyrrolobenzothiadiazole-based organic dyes for efficient dye-sensitized solar cells”, J. Mater. Chem. A, 2014, 2, 15365.
36. J. S. Ni; Y. C. Yen and J. T. Lin, “Organic dyes with a fused segment comprising benzotriazole and thieno[3,2-b]pyrrole entities as the conjugated spacer for high performance dye-sensitized solar cells”, Chem. Commun., 2015, 51, 17080.
37. A. F. Arroyave; C. A. Richard and J. R. Reynolds, “Efficient Synthesis of Benzo[1,2-b:6,5-
b′]dithiophene-4,5-dione (BDTD) and its chemical transformations into precursors for π-conjugated materials”, Org. Lett., 2012, 14, 6138.
38. N. Miyaura; K. Yamada; H. Suginome; A. Suzuki, “Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-
catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes”, J. Am. Chem. Soc., 1985, 107, 972.
39. D. Milstein; J. K. Stille, “A general, selective, and facile method for ketone synthesis from acid chlorides and organotin compounds catalyzed by palladium”, J.Am.Chem.Soc., 1978, 100, 3636.
40. O. Meth-Cohn; S. P. Stanforth, “The Vilsmeier-Haack reaction. In: Trost BM, Fleming I, eds. New York: Pergamon Press”, Comp. Org. Synth., 1991, 2, 777.
41. E. Knoevenagel, “Condensation von Malonsäure mit aromatischen Aldehyden durch Ammoniak und Amine”, Ber. Dtsch. Chem. Ges., 1898, 31, 2596.
42. F. Paul; J. Patt; J. F. Hartwig, “Palladium-catalyzed formation of carbon-nitrogen bonds. Reaction intermediates and catalyst improvements in the hetero cross-coupling of aryl halides and tin amides”, J. Am. Chem. Soc., 1994, 116, 5969.
43. G. Zhang; H. Bala; Y. Cheng; D. Shi; X. Lv; Q. Yu; P. Wang, “High efficiency and stable dye-sensitized solar cells with an organic chromophores featuring a binary π-conjugated spacer”, Chem. Commum., 2009, 2198.
44. Z. Wang; M. Liang; L. Wang; Y. Hao; C. Wang; Z. Sun; S. Xue, “New triphenylamine organic dyes containing dithieno[3,2-b:2',3'-d]pyrrole (DTP) units for iodine-free dye-sensitized solar cells”, Chem. Commun., 2013, 49, 5748.
45. Y. Yang; Y. S. Yen; Y. C. Hsu, H. H. Chou, J. T. Lin, “Organic Dyes Incorporating the Dithieno[3,2-b:2′,3′-d]thiophene Moiety for Efficient Dye-Sensitized Solar CellsOrganic Dyes Incorporating the Dithieno[3,2-b:2′,3′-d]thiophene Moiety for Efficient Dye-Sensitized Solar Cells”, Org. Lett., 2010, 12, 16.
46. S. L. Li; K. J. Jiang; K. F. Shao; L. M. Yang, “Novel organic dyes for efficient dye-sensitized solar cells”, Chem. Commun., 2006, 2792.
47. K. Hara; T. Sato; R. Katoh; A. Furube; Y. Ohga; A. Shinpo; S. Suga; K. Sayama; H. Sugihara; H. Arakawa, “Molecular Design of Coumarin Dyes for Efficient Dye-Sensitized Solar Cells”, J. Phys. Chem. B, 2003, 107, 597.
48. K. Hara; Y. Tachibana; Y. Ohga; A. Shinpo; S. Suga; K. Sayama; H. Sugihara; H. Arakawa, “ Dye-sensitized nanocrystalline TiO2 solar cells based on novel coumarin dyes”, Sol. Energy Mater. Sol. Cells, 2003, 77, 89.
49. P. Gao; H. N. Tsao; M. Gratel and M. K. Nazeeruddin, “Organic Dyes Incorporating the Dithieno[3,2-b:2′,3′-d]thiophene Moiety for Efficient Dye-Sensitized Solar Cells”, Org. Lett., 2012, 14, 4330.
50. X. Wang; L. Guo; P. F. Xia; F. Zheng; M. S. Wong; Z. Zhu, “Dye-sensitized solar cells based on organic dyes with naphtho[2,1-b:3,4-b′]dithiophene as the conjugated linker”, J. Mater. Chem. A, 2013, 1, 13328.
51. Q. Feng; X. Jia; G. Zhou and Z. S. Wang, “A hydride-ligated dysprosium single-molecule magnet”, Chem. Commun., 2013, 49, 7445.
52. R. C. Hiborn, “Einstein coefficients, cross sections, f values, dipole moments, and all that”, Am. J. Phys., 1982, 50, 982.