臺灣博碩士論文加值系統

光敏化染料為染料敏化太陽能電池(Dye-sensitized Solar Cells (DSCs))的核心組成，亦為影響元件光電轉換效能與穩定性之重要關鍵；在眾多光敏化劑中，釕錯合物染料的MLCT (Metal-to-Ligand Charge Transfer)特性具有可使其敏化之元件有效吸收可見光與部份近紅外光等優點，有機會更進一步提高元件的光電流密度與光電轉換效率，因此本研究選擇以含有三吡啶(Terpyridine)固著配位基Black dye (N749)為基礎，設計合成出CYC-36 與 CYC-41兩個新型釕錯合物染料，其設計概念主要是在該固著配位基的吡啶4號位上分別以Pyrrole和首次應用在太陽能領域的Thieno[3,2-b]pyrrole單元取代原先的羧酸基，希望可藉此提高釕錯合物光敏化染料的吸光能力與元件效能。其中CYC-41的MLCT最大吸收波長(max)不僅可紅位移至615 nm (優於Black dye的599 nm)，吸收係數(8800 M-1 cm-1)亦優於Black dye (7500 M-1 cm-1)；搭配碘電解質時，元件的IPCE結果顯示兩新型染料相較於Black dye確實可有效提高電池在波長400到500 nm以及800到900 nm的轉換效能；在TiO2光電極厚度為45 µm與AM 1.5G模擬太陽光照射條件下，CYC-36所敏化之電池元件短路電流密度(Jsc)達17.34 mA cm-2 (優於Black dye的17.13 mA cm-2)，元件光電轉換效率為8.00% (相同條件下Black dye元件為8.93%)，另一方面，CYC-41在搭配TiO2光電極厚度為25 µm條件下，所敏化之電池元件亦較Black dye有較高的Jsc (17.62 mA cm-2 vs. 17.54 mA cm-2)，整體效能達7.82% (相同條件下Black dye元件為8.88%)。除合成兩新型釕錯合物染料外，本研究亦系統性地比較上述三個染料與先前本實驗室開發之CYC-37和CYC-39的光物理與電化學性質以及元件特性，以期能為後續設計高效率釕錯合物染料提供更明確的指引。

In dye-sensitized solar cells (DSCs), photosensitizer is the most important component affecting significantly power conversion efficiency (PCE) and stability of the devices. Among numerous photosensitizers, ruthenium (Ru) complexes sensitizers are very promising to enhance further the performance of devices, due to their metal–ligand charge transfer (MLCT) transition that extends into the red and near-infrared region. In this research, we designed and synthesized two new ruthenium complexes, coded CYC-36 and CYC-41, respectively. Our designing concept is based on Black dye (N749) which contains a terpyridine anchoring ligand. We replaced one carboxyl group at the fourth position of terpyridine ligand with pyrrole and thieno[3,2‑b]pyrrole, respectively. The maximum absorption wavelength (max) of CYC-41 is 615 nm red-shifted over 15 nm than that of Black dye. The molar absorption coefficient of CYC-41 (8800 M-1 cm-1) is also higher than of Black dye (7500 M-1 cm-1). IPCE results show the devices sensitized with CYC-36 and CYC-41 in conjunction with an iodide-based electrolyte can convert more blue and red light photons into electricity than that of Black dye. Moreover, when the thickness of TiO2 is fune-tuned to 45 µm and 25 µm, the Jsc of devices based on CYC-36 and CYC-41 reaches 17.34 mA cm-2 and 17.64 mA cm-2, yielding respectively the PCE of 8.00% and 7.82%. Under the same conditions, the performance of Black dye-based cell is 8.93% and 8.88%, respectively. In addition to the design of two new dyes, we compared systematically the properties and the device characteristics for the three dyes as well as CYC-37 and CYC-39 we developed previously to provide more clues of designing highly efficient ruthenium photosensitizers.

中文摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 VI
表目錄 XII
附錄目錄 XIV
第一章 緒論 1
1-1前言 1
1-2太陽光譜與太陽能電池的光伏參數 1
1-3太陽能電池的發展歷史簡介 5
1-4染料敏化太陽能電池的工作原理 7
1-5染料分子設計相關文獻探討 9
1-5-1釕錯合物之結構設計 12
1-5-2含吡咯單元之染料 30
1-6研究動機 38
第二章 實驗部分 40
2-1實驗藥品 40
2-2中間產物之結構與簡稱 43
2-3合成流程及實驗 47
2-3-1在四號位置溴基取代之三牙酯基的合成 47
2-3-2 Ligand-36-ester之合成 53
2-3-3 Ligand-41-ester之合成 57
2-3-4 釕錯合物CYC-36之合成 64
2-3-5 釕錯合物CYC-41之合成 68
2-4 儀器分析與樣品製備 72
2-5 元件組裝與光電轉換效率量測 80
2-5-1 DSCs元件組裝流程 80
2-5-2 DSCs光電轉換效率量測系統 83
第三章 結果與討論 88
3-1 合成相關探討 88
3-1-1 三牙配位基Ligand-36-ester合成所遇到之問題與解決方法 88
3-1-2 三牙配位基Ligand-41-ester之合成探討 101
3-1-3 CYC-36與CYC-41純化方式探討 103
3-2 釕錯合物染料結構鑑定與光物理性質探討 108
3-2-1 CYC-36與CYC-41染料結構鑑定 108
3-2-2 釕錯合物光物理性質探討 113
3-3 釕錯合物分子軌域理論計算結果 122
3-4 釕錯合物電化學性質與前置軌域位能計算 127
3-5 釕錯合物染料敏化電池的元件性能探討 132
第四章 結論 151
參考文獻 153
附錄 165

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