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

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吳錫章(Shi-Jhang Wu) 查詢紙本館藏

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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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