臺灣博碩士論文加值系統

有機染料部分，我們合成出由pyridinium ylide骨架作為受端(acceptor)與固著基團(anchoring group)組成之新型有機染料NO109-NO111應用於染料敏化太陽能電池(DSSC)中。這些新型受端染料比起pyridine-N-oxide (NO107)與N-(carboxymethyl)-pyridinium (NO108)染料，在優化與開發高效率染料開啟一扇窗。在染料敏化太陽能電池中，NO111染料雙芽螯合(bidentate chelation)於TiO2上，其效率表現是所合成的染料中最高的。
有機金屬染料部分，我們設計了拉電子基官能化之N-heterocyclic carbene (NHC)-pyridine配位基，合成出NHC-pyridine Ru錯合物，即CB102、CB103、DC101與CC321染料。在CB102與CB103染料中，我們由一個線性路徑，合成出NHC-pyridine Ancillary配位基，並且以廉價且快速的合成途徑，來合成Bipyridine Anchoring配位基。在DC101染料中，我們以溶劑效應來控制中間物構型（Conformation），成功達到反應專一性結果。在CC321染料中，我們對於NHC與碳陰離子之Ru錯合物的合成，提供了一個可行的路徑。

A set of new organic dyes (NO109-NO111) consisting of pyridinium ylide skeleton as an acceptor and anchoring group were synthesized and characterized for applications in DSSCs. The comparative study of these new acceptor dyes with the pyridine-N-oxide and N-(carboxymethyl)-pyridinium analogous dyes can open up a window to optimize and develop an efficient dyes. A DSSC of dye NO111 with its bidentate chelation on TiO2 showed the highest efficiency among the synthesized dyes.
We designed new N-heterocyclic carbene (NHC)-pyridine ligands with an electron-withdrawing substituents to construct various Ru complexs, (CB102, CB103, DC101, and CC321.) The NHC-pyridine ancillary ligand utilized in CB102 and CB103 dyes were synthesize through an linear synthetic routes. Also, a simple and cheap synthetic strategy was developed to synthesize the bipyridine anchoring ligand. In case of DC101 dye, we achieved the stereospecificity by utilizing the solvent effect which controls the conformation of the intermediate. In case of CC321 dye, we provid the first synthetic strategy to develope Ru-complex bearing both NHC and carbanion ligands.

摘要------------------------------------------------------------------------------------------i
Abstract-------------------------------------------------------------------------------------ii
目錄----------------------------------------------------------------------------------------iii
圖目錄-------------------------------------------------------------------------------------vi
表目錄------------------------------------------------------------------------------------xiii
符號說明---------------------------------------------------------------------------------xiv
第一章 緒論-------------------------------------------------------------------------------1
1-1 前言----------------------------------------------------------------------------------2
1-2 太陽能電池種類-------------------------------------------------------------------6
1-2-1 矽基太陽能電池------------------------------------------------------------6
1-2-2 III-V族太陽能電池--------------------------------------------------------6
1-2-3 硫族化合物薄膜(thin film chalcogenide)太陽能電池----------------7
1-2-4 染料敏化(dye sensitised)太陽能電池-----------------------------------7
1-2-5 有機型(organic)太陽能電池----------------------------------------------8
1-3 染料敏化太陽能電池-------------------------------------------------------------9
1-3-1 工作原理-------------------------------------------------------------------10
1-3-2 光電參數-------------------------------------------------------------------12
1-4 有機染料發展---------------------------------------------------------------------19
1-5 有機金屬染料發展---------------------------------------------------------------35
1-5-1 輔助配位基(ancillary ligand)修飾-------------------------------------38
1-5-2 固著配位基(anchoring ligand)修飾------------------------------------41
1-5-3 NCS配位基(thiocyanate ligand)修飾---------------------------------43
第二章 Pyridinium ylide系列有機染料--------------------------------------------46
2-1 染料之設計理念------------------------------------------------------------------47
2-2 染料之合成策略------------------------------------------------------------------57
2-3 NO107-NO111染料之合成-----------------------------------------------------59
2-4 NO107-NO111染料之結構鑑定-----------------------------------------------69
2-5 NO107-NO111染料之光物理性質探討--------------------------------------77
2-6 NO107-NO111染料之電化學性質探討--------------------------------------81
2-7 NO107-NO111染料之元件性質探討-----------------------------------------83
2-8 結論---------------------------------------------------------------------------------86
第三章 N-heterocyclic carbene系列有機金屬染料-------------------------------88
3-1 輔助配位基(ancillary ligand)修飾---------------------------------------------89
3-1-1 結構設計理念-------------------------------------------------------------89
3-1-2 CB102與CB103染料之合成-------------------------------------------96
3-1-3 CB102與CB103染料之光物理性質探討--------------------------101
3-1-4 CB102與CB103染料之電化學性質探討--------------------------103 3-1-5 結論------------------------------------------------------------------------105
3-2 固著配位基(anchoring ligand)修飾------------------------------------------106
3-2-1 結構設計理念------------------------------------------------------------106
3-2-2 DC101、DC107與DC108染料之合成------------------------------108
3-2-3 DC101、DC107與DC108染料之光物理性質探討----------------114
3-2-4 DC101、DC107與DC108染料之電化學性質探討----------------116 3-2-5 結論------------------------------------------------------------------------118
3-3 NCS配位基(thiocyanate ligand)修飾----------------------------------------119
3-3-1 結構設計理念------------------------------------------------------------119
3-3-2 CC321染料之合成-----------------------------------------------------123
3-3-3 CC321染料之光物理與電化學性質探討--------------------------127
3-3-4 結論------------------------------------------------------------------------130
第四章 實驗部分----------------------------------------------------------------------131
4-1 NO107-NO111染料------------------------------------------------------------132
4-2 CB102-CB103染料-------------------------------------------------------------143
4-3 DC101、DC107與DC108染料-----------------------------------------------151
4-4 CC321染料----------------------------------------------------------------------156
參考文獻--------------------------------------------------------------------------------163
附錄--------------------------------------------------------------------------------------166

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