臺灣博碩士論文加值系統

本研究之目標是合成以 Triphenylamine 及 Thiophene 衍生物為建構單元之全有機小分子光敏化染料，因為有機小分子與被廣泛使用之釕金屬錯合物，兩者相較之下，有機小分子染料有著較高吸收係數及無須使用貴重金屬元素的好處。我們運用了兩種有機合成法，先以 Vilsmeier-Haack reaction 將 Triphenylamine (TPA)、N,N′-Bis(3-methylphenyl)-N,N′-diphenylbenzidine (TPD)、2,2′-Bithiophene (BT) 及 3,4-ethylenedioxythiophene (EDOT)接上所需的醛基數目，再利用 Knoevenagel condensation reaction，是以 TPA、TPD、EDOT 及 BT 所接上的醛基與
Rhodanine-3-acetic acid 上的亞甲基進行親核性加成反應隨後再進行脫水反應，即
可得我們所需的全有機小分子光敏化染料，隨後再以 Rhodanine-3-acetic acid 上的
羧酸和二氧化鈦奈米粒子進行自組裝作用。此外我們也將此光敏染料運用於電致
色變元件上。分別探討接上不同數目的 Rhodanine-3-acetic acid 之染料組成染料敏
化太陽能電池與電致色變元件的效能差異。

Triphenylamine (TPA,TPD)- and ethylene dioxyl thiophene (EDOT,BT)-based metal-free organic dyes were synthesized and employed to the dye-sensitized solar cells (DSSCs) in this study. Metal-free organic dye, compared to the ruthenium-based photo-sensitizer in the dye-sensitized solar cells, has the advantages of high absorbance coefficient and without using expensive metal. We employed two kinds of organic synthetic methods. Different number of aldehyde groups were first linked on the molecules of TPA,EDOT,EDOT and BT by using the Vilsmeier-Haack reaction. Then, the metal-free organic dyes were obtained through the nucleophilic addition and dehydration between the aldehyde groups on TPA,EDOT,EDOT and BT and the methylene of rhodanine-3-acetic acid by using the Knoevenagel condensation reaction. The two dyes were anchored on the surface of titanium dioxide nanoparticles using the carboxylic acid of dyes by means of the self-assembly method. Furthermore, these dyes were also used to assemble the electrochromic device. A vertical integration of dye-sensitized solar cells and electrochromic devices was fabricated and subjected to measure the performance of the integrated devices.

中文摘要………….…………………………...…………………………………………i
Abstract………….…………………………….…………………………………...……ii
致謝………………………………………….……………………...…………………..iii
目錄……………………………………………………….………...…………………..iv
表目錄……………………...………………...…………………..………………...….viii
圖目錄……………………….…………………………………….….……………….. ix
反應機制與流程圖目錄…………………….……………….…...…………………xvii
第一章 緒論…………………………………………………………………………….1
1-1 前言………………………………….………………...………………………1
1-2 染料敏化太陽能電池（Dye-sensitized solar cells，DSSC）之研究發展...........2
1-3 電至色變之簡介………………...…….………...……………...………..……4
1-4 研究動機和目的………………………………………………...…….....……4
1-5 研究架構………………………………………………………...……..……...5
第二章 文獻回顧…………………………………..……………………...…………....6
2-1 染料敏化太陽能電池之構造與工作原理…………….………...………...….6
2-2 二氧化鈦簡介…………………………………………………….…………...7
2-3 染料/敏化劑…………………………………………………………………...8
2-3-1 釕金屬錯合物染料光敏化劑...………………………………………..9
2-3-2 有機高分子染料光敏化劑..……………………….…………………11
2-3-3 有機小分子染料光敏化劑…………………………………………...12
2-3-3-1 Vilsmeier -Haack reaction...……………………...…………14
2-3-3-2 Knoevenagel condensation reaction…......………...………...14
2-4 電解液………………………………………………………..……...……….15
2-5 相對電極……………………………………………………..……...……….16
2-6 電致色變原理……………………………………………...…..…………….16
2-7 電致色變元件之設計……………………………………...…..…………….17
2-8 電致色變元件之應用……………………………………...…..…………….18
第三章 實驗部分……..…………………………………………….…………………20
3-1 儀器與設備……………………………………………….....……………….20
3-2 實驗藥品…………………………………………………….……………….21
3-3 光敏化有機染料之合成步驟與儀器分析 …….…………...………………22
3-3-1 含 Triphenylamine 衍生物及 Thiophene 衍生物的光敏化有機染
料之合成……………...………………...…….……...……….……...22
3-3-1-1 Vilsmeier reagent 之製備………...………………....….………...26
3-3-1-2 4-Formyltriphenylamine 之合成…………………......….………...26
3-3-1-3 4,4′-Diformyltriphenylamine 之合成………………......….……...26
3-3-1-4 4,4′,4′′-Triformyltriphenylamine 之合成…………...…......……27
3-3-1-5 3,4-ethylenedioxythiophene- 2-carbaldehyde之合成….........27
3-3-1-6 3, 4-ethylenedioxythiophene-2,5-Bis(carbaldehyde)之合成...…28
3-3-1-7 2,2′-Bithiophenyl-5-carbaldehyde 之合成…......…………….…28
3-3-1-8 2,2′-Bithiophenyl-5,5′-dicarbaldehyde之合成…..............…29
3-3-1-9 TPD-aldethyde 之合成....................................29
3-3-1-10 TPAR1 之合成.............................30
3-3-1-11 TPAR2 之合成..........................................30
3-3-1-12 TPAR3 之合成..........................................31
3-3-1-13 EDOTR1 之合成.............................................31
3-3-1-14 EDOTR2 之合成.....................................31
3-3-1-15 BTR1 之合成........................................32
3-3-1-16 BTR2 之合成..........................32
3-3-1-17 TPDR 之合成.............................32
3-3-2 性質鑒定……………………………………………..………………….33
3-3-2-1 液態核磁共振光譜儀（Solution state Nuclear Magnetic Resonan-
-ce，400MHz）……………..……….……..…………….….……...33
3-3-2-2 傅立葉轉換紅外光譜儀（FT-Infrared Spectrometer）…..………..33
3-3-2-3 紫外光/可見光吸收光譜儀（Ultraviolet/Visible Absorption Sp-
-ecroscopy）…………………….……...…..……………………...34
3-3-2-4 電化學分析儀（AUTO-LAB Electrochemical Instrument）....…34
3-4 染料敏化太陽能電池及電致色變之製備與元件組裝.…………………….34
3-4-1 導電玻璃的前處理………………….…………………………………..34
3-4-2 二氧化鈦薄膜電極之製備……………………………………………...35
3-4-2-1 TiO2 paste 製備…………………………………………………...35
3-4-2-2 薄膜厚度測定儀（α-step）………………………………………...35
3-4-3 敏化染料的吸附………………………………………………………...35
3-4-4 元件之電解質溶液的配製……………………………………………...36
3-4-5 白金相對電極製作 ……………………………………...…………..…36
3-4-6 染料敏化太陽能電池之組裝…………………………………………...36
3-4-7 電製色變元件之組裝及光譜電化學研究……………………………...39
第四章 結果與討論……..…………………………………..………………...………38
4-1 染料中間體及最終產物之合成……………………………………...……...38
4-2 染料中間體及最終產物之結構鑑定………………………………...……...38
4-2-1 液態核磁共振光譜儀(NMR)鑑定分子結構…………………………...38
4-2-2 傅立葉紅外線光譜儀(FTIR)鑑定官能基………………….…...……...60
4-3 三苯胺基結構之光敏染料應用於電變色元件與光敏化染料太陽能電池
之探討………………………………...…….……………...…..…….……...66
4-3-1 三苯胺基結構之光敏染料之光學性質分析………...………….……...66
4-3-1-1 光敏染料之紫外光/可見光(UV/VIS)光譜分析..……...….………....66
4-3-1-2 TiO2 薄膜已吸附染料與未吸附之紫外光/可見光(UV/VIS) 吸收光
譜…………………………………………………………………...66
4-3-2 TPAR1 及PTPAR1 染料之能隙變化………...……...…...…….……...69
4-3-3 三苯胺基結構染料之電化學分析………...……….………...................70
4-3-4 三苯胺基結構之染料之光譜電化學特性………...………….………...73
4-3-4 單層元件之電致色變特性………...……….…………………………...75
4-3-5 三苯胺基結構之染料之固態電致色變元件(ECD) …………....……...77
4-3-6 三苯胺基結構之染料電池光電轉化效率測試………...……….……...88
4-4 噻吩基結構之光敏染料應用於電變色元件與光敏化染料太陽能電池之
探討………..………………………………………………………………...90
4-4-1 噻吩基結構之光敏染料之光學性質分析…………………………...90
4-4-1-1 光敏染料之紫外光/可見光(UV/VIS)光譜分析……………...…...90
4-4-1-2 TiO2 薄膜已吸附染料與未吸附之紫外光/可見光(UV/VIS) 吸收光
譜……………………………………………………………....…...90
4-4-2 噻吩基結構染料之電化學分析………………………………………...93
4-4-3 噻吩基結構之染料之光譜電化學特性………………………………...95
4-4-4 單層元件之電致色變特性……………………………………..……….96
4-4-5 噻吩基結構之染料之固態電致色變元件(ECD) ………………......….98
4-4-6 噻吩基結構之染料電池光電轉化效率測試………………………….107
第五章 結論與未來工作……..……………………………..…………………….…109
第六章 参考文獻…………..………………………..…………………………….…110

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