臺灣博碩士論文加值系統

在本論文中分為兩個部分進行探討，皆為改良black dye (N749) 結構之三牙配位釕金屬錯合物。
第一部分為一系列全光域吸收的釕金屬錯合物，以thiophene官能團修飾isoquinoline pyrazolate作為雙牙配位基、thiocyanate單牙配位基、三牙配位的terpyridine作為錨基，並將2-dodecylthienyl取代基修飾在isoquinoline的不同位置上，此系列染料在光譜的400~800 nm的分子吸收係數明顯高於比對染料black dye，使其在可見光及紅外光的部分擁有更佳的光捕獲性質，提升了元件效率表現。
第二部分為具高穩定性、無thiocyanate配位基的雙三牙釕金屬錯合物，利用三牙結構的配位基不但可以避免像thiocyanate具異構物，使合成產率提升，且在元件上擁有較好的長效性。並以烷基官能團取代過去常用之高共軛官能團，降低合成複雜度與原料、人事成本，提升商業化可行性，並做不同烷基官能團的修飾對元件表現的影響，最後對此系列染料做長效測試及成本分析。

This work separated into two parts, both of them improved from the structure of black dye (N749).
In part I, here reports a new series of panchromatic Ru(II) terpyridine sensitizers which possess thienyl functionalized isoquinoline pyrazolate chelates, along with tridentate terpyridine anchor and monodentate thiocyanate ligand. The 2-dodecylthienyl substituent was modified at various sites of isoquinoline moiety. These new sensitizers exhibit significantly higher molar extinction coefficients at 400-800 nm versus N749 reference complex, leading better light-harvesting capability across visible and near infrared region (NIR), giving a superior performance to DSC cells.
In part II, A series of bis-tridentate and thiocyanate-free Ru(II) sensitizers with high stability were designed. Tridentate ligands were substituted for three thiocyanate ligands, which not only avoided thiocyanate linkage isomerism to increase the yield but also enhanced the lifespan of as-fabricated solar cell device. Different from previous extended-conjugation structure, here attached small alkyl groups to azolate chelates to reduce synthesis process and cost, leading to more opportunities for commercial application. Moreover, different alky-substituted tridentate chelates showed different device performance. At last, the stability test and synthesis cost analysis has been done.

摘要 i
第一章、序論 1
第一節、前言 1
第二節、DSSC基本工作原理 4
第三節、DSSC元件結構與組成 6
1-3-1. TiO2光陽極： 6
1-3-2. 染料分子 (dye)： 8
1-3-3. 電解液 (electrolyte)： 8
1-3-4. 對電極 (counter electrode)： 12
1-3-5. 透明導電薄膜 (transparent conducting film, TCO)： 14
第四節、DSSC元件參數 15
1-4-1. 基本光電參數 15
1-4-2. 電子在TiO2的傳輸及復合 18
1-4-3. 染料藉電解液的再生與還原 19
第五節、DSSC染料發展 20
1-5-1. 純有機染料 21
1-5-2. 以Zn為中心金屬仿葉綠素的紫質染料 24
1-5-3. 有機金屬錯合物染料 26
第六節、研究動機 42
第二章、分析儀器與實驗步驟 43
第一節、分析儀器 43
1. 核磁共振光譜 (Nuclear Magnetic Resonance, NMR) 43
2. 質譜分析 (Mass Spectrometer, MS) 43
3. 元素組成分析 (Elemental Analysis, EA) 43
4. 紫外-可見光光譜儀 (Ultraviolet-Visible Spectrometer, UV-Vis) 44
5. 螢光光譜儀 (Fluorescence Spectrophotometer, PL) 44
6. 循環伏安法 (Cyclic Voltammeter, CV) 44
7. 暫態光電流與電壓量測系統 (恆電位儀, Autolab) 44
8. 電流-電壓曲線量測 (J-V Curve Measurement) 45
9. 入射光電轉化效率 (IPCE Measurement) 45
第二節、配位基合成 46
2-2-1. 合成 (L1) 46
2-2-2. 合成 (L2) 51
2-2-3. 合成 (L3) 53
2-2-4. 合成 (L4) 57
2-2-5. 合成 (L5) 58
2-2-6. 合成 (L6) 59
第三節、錯合物合成 61
2-3-1. 合成PRT-31~33系列Ru(L)(H2tctpy)(NCS) 錯合物 61
2-3-2. 合成TF系列Ru(L)(H3tctpy) 錯合物 65
第四節、染料敏化太陽能電池元件製作 68
2-4-1. TiO2 奈米粉體及其漿料製備 68
2-4-2. 光陽極 68
2-4-3. Pt 對電極 69
2-4-4. 電解質 69
2-4-5. 元件組裝 69
第三章、結果與討論 70
第一部分、PRT系列 Ru(L)(H3tctpy)(NCS) 錯合物 70
3-1-1. 染料設計概念與合成鑑定 70
3-1-2. PRT-31~33系列光物理性質 76
3-1-3. PRT-31~33系列電化學性質與能階圖 79
3-1-4. PRT-31~33系列元件製備與探討 81
第二部分、TF系列Ru(L)(H3tctpy) 錯合物 89
3-2-1. 染料設計概念與合成鑑定 89
3-2-2. TF系列光物理性質 91
3-2-3. TF系列電化學性質 94
3-2-4. TF系列元件製備與探討 96
3-2-5. TF系列元件長效穩定性探討 101
3-2-6. TF-tBu優勢分析 103
第四章、結論 111
第五章、未來展望 112
參考文獻 113

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