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姓名 吳錫章(Shi-Jhang Wu)  查詢紙本館藏   畢業系所 化學學系
論文名稱 應用於染料敏化太陽能電池之新型釕金屬錯合物的合成與性質探討
(A Novel Ruthenium-Based Photosensitizer for Dye-Sensitized Solar Cells)
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摘要(中) 本研究主要合成二個新的含雙吡啶配位基之釕金屬錯合物:SJW-E1以及CYC-B3,並探討其物理性質及在染料敏化太陽能電池(Dye-Sensitized Solar Cells, DSCs)中作為光敏劑的應用。兩錯合物最大的差異在於輔助配位基 (ancillary ligand)的不同,其中CYC-B3為alkyl-thiophene,而SJW-E1則是使用alkyl-ethylenedioxythiophene。二個錯合物皆採用One-pot的合成法合成,並利用NMR、IR與Mass鑑定其結構。亦利用理論計算 (Semi-empirical ZINDO/1)得知錯合物之HOMOs與LUMOs的定域性 (Localization),以剖析Frontier orbitals 的位置與錯合物吸光性質之關連性。在AM1.5光源照射下,以SJW-E1以及CYC-B3敏化之電池元件的光電轉換效率分別為9.02 %與7.39 % (相較於N3電池的8.42 %)。而SJW-E1效率比CYC-B3高,是因為SJW-E1的輔助配位基上的ethylene-dioxy group可以提供額外的共軛系統到噻吩上,使其最大吸收波長紅位移且吸收係數亦增加。ethylene-dioxy group的另一個功能是其為好的電子供給者,可避免染料激發後電子電洞再結合。
摘要(英) Two new ruthenium complexes (SJW-E1, and CYC-B3) with the general chemical formula of [Ru(dcbpy)(L)(NCS)2] where dcbpy is 4,4’-dicarboxylic acid-2,2’-bipyridine and L is 4,4’-bis-(4’-octyl-3,4- ethylenedioxythiophene-2-yl)-2,2’-bipyridine or 4,4’-bis-(4’-octyl-tri- thiophen-2-yl)-2,2’-bipyridine were prepared and well characterized. The performance of these two dye sensitized dye-sensitized solar cells (DSCs) was also explored. These complexes were synthesized via the typical one-pot synthesis and identified with NMR, IR and Mass spectroscopies. In addition, the localizations of HOMOs and LUMOs of these Ru-complexes were calculated with the semi-empirical computation (ZINDO/1) in order to understand the effects of the frontier orbitals on the light harvesting capability of the photosensitizers. Under the illumination of AM1.5 stimulated light, the photon-to-current conversion efficiency of SJW-E1 and CYC-B3 sensitized cells was 9.02 % and 7.39 % whereas 8.42 % is obtained for the N3 sensitized cell. The efficiency of SJW-E1 sensitized solar cell is higher than that of CYC-B3 sensitized solar cell, because of the ethylene-dioxy group on the ancillary ligand of SJW-E1 is able to offer extra conjugated length to thiophene. Therefore, the SJW-E1 has its λmax more red-shifted and higher absorbance coefficient compared to CYC-B3. In addition, the ethylene-dioxy group could avoid electron-hole recombination due to its good electron donating ability. These characteristics make SJW-E1 a good photesensitizer for DSCs.
關鍵字(中) ★ 染料敏化太陽能電池
★ 錯合物
★ 光敏化劑
關鍵字(英) ★ Dye-Sensitized Solar Cells
★ Complexes
★ Photesensitizer
論文目次 摘要………………………………………………………………….…i
Abstract.................................................................................................ii
謝致.........................................................................................................iii
目錄.........................................................................................................iv
圖目錄....................................................................................................vii
表目錄......................................................................................................x
流程圖目錄.............................................................................................xi
壹.序論
1-1、前言.............................................................................1
1-2、太陽能電池的種類.....................................................2
1-3、染料敏化太陽能電池之研究發展(Dye-Sensitized Solar Cells,DSC)......................................................3
1-4、染料敏化太陽能電池之工作原理.............................5
1-5、光電轉換效率(η(%))的量測.............................7
1-6、光敏化劑 – 染料......................................................10
1-7、輔助配位基(ancillary ligand)的修飾......................14
貳.實驗部分
2-1實驗藥品.......................................................................22
2-2、儀器分析與樣品製備................................................25
2-2-1、紫外光/可見光/近紅外光吸收光譜儀 (UV/VIS/NIR Spectrometer).......................................................................25
2-2-2、紅外光吸收光譜儀 (FT-IR Spectrometer).........................26
2-2-3、核磁共振光譜儀 (NMR)....................................................27
2-3、合成步驟
2-3-1、4,4-dibromo-2,2-bipyridine的合成..................................28
2-3-1-1、[2,2′]Bipyridinyl 1.1′-dioxide 的合成............................29
2-3-1-2、4,4′-Dinitro-〔2,2′〕bipyridinyl 1,1′-dioxide的合成.....29
2-3-1-3、4-4’-Dibromo-2,2’-bipyridine-1,1’-dioxide的合成........30
2-3-1-4、4-4’-dibromo-2,2’-bipyridine的合成..............................31
2-3-2、4-(2,3-dihydro-5-octylthieno[3,4-b][1,4]dioxin-7-yl) -2-(4(2,3-dihydro-5-octylthieno[3,4-b][1,4]dioxin-7-yl) pyridin-2-yl) pyridine (doetbpy)的合成...........................34
2-3-2-1、2,3-dihydro-5-octylthieno[3,4-b][1,4] dioxine (OEDOT)
的合成...............................................................................35
2-3-2-2、TMeSn-OEDOT的合成...................................................36
2-3-2-3、doetbpy的合成.................................................................37
2-3-3、4-(5-octylthiophen-2-yl)-2-(4(5-octylthiophen- 2-yl) pyridin-2-yl)pyridine (dotbpy)的合成..............................38
2-3-3-1、2-octyl-thiophene(OT)的合成..........................................39
2-3-3-2、TMeSn-OT的合成...........................................................40
2-3-3-3、dotbpy的合成...................................................................41
2-3-4、釕錯合物(SJW-E1)的合成.................................................44
2-3-5、釕錯合物(CYC-B3)的合成................................................47
2-4、電極製備與元件組裝.............................................................51
参.結果與討論
3-1、SJW-E1及CYC-B3的合成與結構鑑定................................53
3-2、SJW-E1與CYC-B3吸光性質的探討..................................57
3-3 SJW-E1與CYC-B3的分子軌域理論計算探討…………..59
3-4、SJW-E1與CYC-B3的能階探討..........................................62
3-5、錯合物染料之異構物對其吸收係數及所組成電池元件 之光電轉換效率的影響的探討...........................................65
3-6、使用SJW-E1與CYC-B3作為敏化劑組裝成電池的效能探討............................................................................................68
3-7、電化學阻抗的分析.................................................................72
肆.結論...........................................................74
伍.參考文獻.......................................................75
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指導教授 吳春桂(Chun-Guey Wu) 審核日期 2007-7-17
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