尋找應用於染料敏化太陽能電池之藍色染料｜國立中央大學博碩士論文系統

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研究生：	徐子閎 Tzu-Hung Hsu
論文名稱：	尋找應用於染料敏化太陽能電池之藍色染料
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：	2017
畢業學年度：	105
語文別：	中文
論文頁數：	129
中文關鍵詞：	染料敏化太陽能電池、藍色染料
相關次數：	點閱：13 下載：0
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染料敏化太陽能電池（dye-sensitized solar cells, DSC）由於具有多色彩性、半透光性、可撓曲性與低製造成本等優點，是目前相當熱門的研究領域之一。而應用在染料敏化太陽能電池之藍色染料較少見。本實驗室先前合成出以benzothienoisoindigo (BTI)單元為輔助拉電子基的BTI-3、BTI-5和BTI-6皆因最大吸收波長太長，在DMSO中呈現藍綠色。本研究是以BTI-3作為基本結構出發，將BTI單元中的Thiophene由靠近於推電子基改為靠近於拉電子基，設計出BTI-4，使其最大吸收波長藍位移。再來以BTI-3及BTI-5作為基本結構，分別在推電子基及輔助拉電子基（Aa）中間插入一個苯環，合成出BTI-7及BTI-13，藉由染料的平面性下降而使最大吸收波長藍位移。再以BTI-13為基本結構，將推電子基換成正己基或溴基，設計出BTI-15和BTI-17，利用較弱的推電子基及降低染料分子的共軛長度，使染料之最大吸收波長藍位移。結果顯示BTI-4在DMSO中之最大吸收波長比BTI-3短，呈現較接近藍色的藍綠色。BTI-7和BTI-13的最大吸收波長都比相對的BTI-3及BTI-5的短，在DMSO中也都呈現藍綠色，但比BTI-3及BTI-5更接近藍色。BTI-15及BTI-17在DMSO中的顏色比BTI-13更接近藍色，其中含最弱推電子基的BTI-17呈現深藍色。而將染料吸附在TiO2後，因其最大吸收波長產生藍位移，BTI-4與BTI-7呈現綠色，BTI-13、BTI-15與BTI-17之元件呈現紅色。雖然BTI系列染料的LUMO能階都不高，但可透過電解質優化，使TiO2的導帶能階下降，提高染料受光激發的電子注入至TiO2導帶能階的驅動力。其中，有最高莫耳吸收係數乘以染料吸附量和吸附在TiO2有高覆蓋度的BTI-13所組裝之元件有最高的光電轉換效率達4.41%。

Dye-sensitized solar cell (DSC) is a hot research topic because of its multicoloured, semi-transparent, flexible and low cost. A lot of studies are related to find new sensitizers nevertheless blue dye is relatively rare. In this thesis, we focus on the synthesis of blue dyes for DSC. Our previous study showed that BTI-3, BTI-5 and BTI-6 with benzothienoisoindigo (BTI) unit as an auxiliary acceptor (Aa) are blue-green in DMSO due to their λmax values are too long. To blue-shift the λmax of the dyes, BTI-4 is design by changing the position of acceptor part to be connected to the thiophene of BTI unit instead of connecting to the benzene. The λmax value of BTI-4 is smaller than that of BTI-3, but still in blue-green when dissolved in DMSO. BTI-7 and BTI-13 are prepared by inserting an additional phenyl unit between donor and Aa of BTI-3 and BTI-5, respectively. The λmax values of both BTI-7 and BTI-13 are smaller than those of BTI-3 and BTI-5. However, the color of BTI-7 and BTI-13 in DMSO is still blue-green. Finally we prepared BTI-15 and BTI-17 by using n-hexyl and bromide as donor instead of fluorene, respectively. The λmax value of BTI-15 is blue-shifted in DMSO but the color is still blue-green, nevertheless BTI-17 in DMSO is blue. BTI-4 and BTI-7 adsorbed on TiO2 film is green, BTI-13, BTI-15, and BTI-17 adsorbed on TiO2 film is red. These five dyes were used as sensitizers for DSC, BTI-13 has the highest conversion efficiency of 4.41%, due to its high molar absorption coefficient and large dye loading which leads to high surface coverage of when adsorbed on TiO2 film.

摘要    I
Abstract    II
摘要圖    III
謝誌    IV
圖目錄    IX
表目錄    XIII
壹、序論    1
1-1、前言    1
1-2、太陽能電池的種類    1
1-3、染料敏化太陽能電池簡介    2
1-4、光電轉換效率（η）的量測    4
1-4-1、標準太陽光    4
1-4-2、光電轉換效率（η）    5
1-4-3、外部量子產率（External Quantum Efficiency, EQE）    6
1-5、用於染料敏化太陽能電池中之染料的特性    7
1-5-1、無機染料    7
1-5-2、紫質染料    9
1-5-3、有機染料    10
1-6、染料之顏色    12
1-6-1、染料敏化太陽能電池的色彩    12
1-6-2、色彩學    13
1-7、應用於DSC之藍色染料    13
1-7-1、以diketopyrrolopyrrole (DPP)為輔助拉電子基（Aa）之藍色染料    14
1-7-2、以[1,2,5]Thiadiazolo[3,4-c]pyridine為輔助拉電子基之藍色染料    16
1-8、應用於太陽能電池之含Isoindigo單元的分子    17
1-9、應用於太陽能電池之含Benzothienoisoindigo單元的分子    20
1-9-1本實驗室先前以Benzothienoisoindigo單元設計出的DSC染料    22
1-10、在染料分子的推電子基與輔助拉電子基之間插入苯環使染料之最大吸收波長變短及提高LUMO能階    24
1-11、研究動機    26
貳、實驗部分    28
2-1、實驗藥品    28
2-2、產物與中間產物之結構與簡稱    30
2-3、實驗步驟    37
2-3-1、Carbazole-Et-B的合成，如Scheme 2.1所示    37
2-3-2、BTI-2R-Br的合成，如Scheme 2.2所示    39
2-3-3、BTI-4的合成，如Scheme 2.3所示    41
2-3-4、Br-BTI-Ph-CHO的合成，如Scheme 2.4所示    44
2-3-5、BTI-7的合成，如Scheme 2.5所示    46
2-3-6、BTI-13的合成，如Scheme 2.6所示    48
2-3-7、BTI-15的合成，如Scheme 2.7所示    50
2-3-8、BTI-17的合成，如Scheme 2.8所示    52
2-4、儀器分析與樣品製備    53
2-4-1、核磁共振光譜儀（Nuclear Magnetic Resonance）    53
2-4-2、紫外光/可見光吸收光譜儀（UV/Vis Spectrometer）    53
2-4-3、螢光分光光譜儀（Fluorescence Spectrophotometer）    54
2-4-4、電化學測量裝置（Electrochemical Measurement System）    55
2-4-5、太陽光模擬器與元件I-V曲線量測系統（Solar Simulator and I-V measuring system）    56
2-4-6、太陽能電池外部量子效率量測系統（Incident Photon to Current Conversion Efficieny, IPCE measurement）    57
2-4-7、交流阻抗分析﹙Electrochemical-Impedance Analysis, EIS﹚    57
參、結果與討論    60
3-1、合成BTI系列染料遭遇之問題    60
3-1-1、Car-BTI-Br之合成    60
3-1-2、BTI-4之合成    61
3-2、BTI系列染料之光學性質探討    61
3-3、BTI系列染料之前置軌域能階    67
3-4、BTI系列染料的前置軌域分布    72
3-5、以BTI-4、BTI-7、BTI-13、BTI-15與BTI-17染料所敏化之DSC元件的光電表現探討    75
3-6、以 BTI-4、BTI-7、BTI-13、BTI-15與BTI-17染料組裝之DSC元件的電化學阻抗（Electrochemical impedance spectroscopy, EIS）分析    78
肆、結論    80
伍、參考文獻    81
附錄    86
附錄1、DSC元件的組裝    86
附錄2、以 BTI-4、BTI-7、BTI-13、BTI-15、BTI-17染料來組裝DSC元件時的電解質優化步驟    87
附錄2-1、電解質中tBP濃度對元件光電轉換效率的影響    87
附錄2-2、電解質中LiI濃度對元件光電轉換效率的影響    88
附錄2-3、電解質中BMII濃度對元件光電轉換效率的影響    90
附錄2-4、電解質中GuSCN濃度對元件光電轉換效率的影響    93
附錄3、BTI系列染料於TiO2的吸附量之量測    95
附錄4、UV-Vis吸收光譜圖與螢光光譜圖之疊圖    96
附錄5、1H-NMR圖譜    97

                                

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