應用於染料敏化太陽能電池之金屬錯和物固著配位基的合成

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研究生：	洪仁超 Ren-Chau Hung
論文名稱：	應用於染料敏化太陽能電池之金屬錯和物固著配位基的合成
指導教授：	吳春桂 Chun-Guey Wu
口試委員:
學位類別：	碩士 Master
系所名稱：	理學院 - 化學學系 Department of Chemistry
論文出版年：	2013
畢業學年度：	101
語文別：	中文
論文頁數：	69
中文關鍵詞：	染料敏化太陽能電池、固著配位基、噻唑
外文關鍵詞：	DSSC, anchroing, thiazole
相關次數：	點閱：10 下載：0
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太陽能是一個不受地形影響、乾淨且儲量豐富的能源，要把太陽光能轉換成電能就需要使用太陽能電池。其中第三代太陽能電池中的染料敏化太陽能電池( DSSC) ，為現在太陽能電池的研發重點之一。以釕金屬錯合物作為DSSC的光敏劑有不錯的光電效率表現，本篇論文主要是開發釕金屬錯合物的固著配位基。過去開發固著配位基的文獻，雖然都成功地使元件的光電流值( Jsc)提升，但開路電壓(Voc)下降，使得元件整體的光電轉換效率並沒有顯著的提升，因此開發出一個可以提升染料的吸光能力並同時提升Voc的固著配位基為本篇論文的重點:其做法為在固著配位基的 bipyridine及 COOH間引入噻唑(thiazole)單元，合成出 Ligand 50，利用噻唑擁有比噻吩更好的拉電子能力，使染料的 LUMO軌域主要集中在固著配位基；當染料受光激發時，大部分的電子可以經由固著配位基注入二氧化鈦，提高二氧化鈦的費米能階(femi level)，增加元件之 Voc。本篇論文探討 Ligand 50的合成路徑以及合成時中間所遭遇到的問題。

Solar energy is a clean and abundant energy. Solar cells is a device to convert solar energy to electricity. Dye sensitized solar cells (DSSCs), one of the 3rd generation solar cells, has been investigated extensively in the part 3 decades. Ruthenium complex photosensitizer has a good efficiency. This thesis focus majorly in developing new anchoring ligand of Ruthenium complex. Past studies showed that extention the conjugation length of the anchoring ligands was successfully increased the short-circuit photocurrent density(Jsc), however the open-circuit voltage (Voc) decreased. Therefore searching for the anchoring ligand which can improve the absorption coefficient of Ru-based dye and also improve Voc of the corrospondly device, is the goal of this thesis. A thiazole unit was inserted between bipyridine of the anchoring ligand to form the Ligand 50. Thiazole the better electron withdrawing moiety compare to thiophene, dye molecule incorporate a thiazole moiety in the anchoring ligand make the LUMO distribute more in the anchoring ligand. Therefore when the dye was excited by light, the electrons can more to the anchoring ligand then inject into titania dioxide. Life the femi-level of titania dioxide, increase the Voc of device. This thesis mainly discussed the prepartion of Ligand 50 and the problem during the synthesis.

目錄
中文摘要..................................................I
英文摘要..................................................II
目錄......................................................III
圖目錄....................................................VI
表目錄..................................................VIII


壹、序論..................................................1
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的組成與工作原理...................3
1-4、光電轉換效率（η）的量測.............................5
1-4-1、IPCE （incident photon to current conversion efficiency）..............................................6
1-4-2、總光電轉換效率( η ) ..............................7
1-5、釕金屬光敏化劑.......................................8
1-6、本實驗室的輔助配位基(ancillary ligand)的設計.........11
1-6-1、本實驗室的輔助配位基的設計:增加共軛單元............11
1-6-2、本實驗室的輔助配位基的設計:使用electron-donor group.13
1-6-3、固著配位基(anchoring ligand)的研究.................16
1-6-3-1、固著配位基的設計：增加共軛單元...................18
1-7、研究動機.............................................29


貳、實驗部分...............................................30
2-1、實驗藥品..............................................30
2-2、儀器分析與樣品製備....................................33
2-2-1、核磁共振光譜儀 (NMR) ...............................33
2-3、合成步驟..............................................34
2-3-1、ligand-B11的合成....................................34
2-3-2、Ligand 50的合成.....................................35
2-3-2-1、2-(trimethylsilyl)thiazole (2-TST)的合成..........36
2-3-2-2、2-trimethylsilyl-5-trimethylstannylthiazol (2-ST-5TMSn-T)的合成.............................................37
2-3-2-3、5-trimethylstannylthiazol (5TMSn-T)的合成.........38
2-3-2-4、4-4’Bithiazol-bipyridine (4-4’BTBPy)的合成......39
2-3-2-5、Ethyl 5-ethoxycarbonyl-4,4'-bithiazol-bipyridine( Ligand 50)的合成...........................................41

参、結果與討論.............................................43
3-1、Ligand 50的合成設計...................................43
3-1-1、本研究失敗的合成步驟探討............................45
3-1-1-1、2-thiazolecarboxylic acid ethyl ester(2-OEtT)的合成.........................................................45
3-1-1-2、ethyl 5-(trimethylstannyl)thiazole-2-carboxylate(5-TSn-2OEtT)的合成........................................46
3-1-1-3、ethyl 5-(trimethylstannyl)thiazole-2-carboxylate(5-TSn-2OEtT)的合成(2).......................................48
3-1-1-4、ethyl 5-(trimethylstannyl)thiazole-2-carboxylate(5-TSn-2OEtT)的合成(3).......................................50
3-1-1-4、ethyl 5-(trimethylstannyl)thiazole-2-carboxylate(5-TSn-2OEtT)的合成(4).......................................52
3-1-2、Ligand 50 的合成設計(2)............................53
3-1-2-1、由4-4’BTBPy 合成Ligand 50的條件探討.............54
3-1-2-1-1、由4-4’BTBPy 合成Ligand 50的條件探討:拔氫步驟時的
反應溫度..................................................56
3-1-2-1-2、由4-4’BTBPy 合成Ligand 50的條件探討:拔氫使用的
鹼........................................................58
3-1-2-1-3、由4-4’BTBPy 合成Ligand 50的條件探討:拔氫使的反應時間......................................................60

肆、結論..................................................63
伍、參考文獻..............................................64


                                

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