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研究生： 山地普
Sandeep Mane
論文名稱： 環修飾之紫質的設計與合成以應用於太陽能光敏染
Design and Synthesis of Core-modified Porphyrin Sensitizers for Dye-Sensitized Solar Cells
指導教授： 洪政雄
Hung, Chen-Hsiung
學位類別： 博士
Doctor
系所名稱： 化學系
Department of Chemistry
論文出版年： 2014
畢業學年度： 102
語文別： 英文
論文頁數： 263
中文關鍵詞： 太陽能光敏染料 、環修飾紫質 、大環紫質 、硼配位的oxasmaragdyrins
英文關鍵詞： Dye-sensitized solar cells, core-modified porphyrins, expanded porphyrins, organic dyes
論文種類： 學術論文
相關次數： 點閱：57  下載：0 
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    • 此篇論文報導了新的環修飾紫質以及大環紫質的設計與合成，以及其在太陽能光敏染料之應用。此些染料的發展由單硫取代紫質以及單氧取代紫質開始，並且其上有一ethynylphenyl 基團為共振鏈以及以羧基為掛載基團。比較這些異原子取代紫質與傳統的四氮紫質，結果顯示異原子的取代降低了這些染料的光電伏打效率，其中單氧取代的紫質表現更低於單硫取代的紫質。接著我們對單硫取代紫質進行了環修飾得到了擁有A3B以及A2B2之不同取代型式的五種衍生物。經由光物理和電化學的研究顯示以ethynylphenyl基團延伸共振的鏈長不僅增加了環的平面性，同時也增加了光譜的紅位移。而在取代基上加上擁有拉電子能力的cyano基團亦可增加分子的極性而讓分子有較佳的電荷轉移效果。結合上訴修飾，單硫取代紫質的光電轉換效率可由沒有cyano基團的0.2 % 提升到有cyano基團的1.69 %。
    我們亦致力於研究大環紫質於太陽能光敏染料的應用。我們合成出了有硼配位的oxasmaragdyrins，其是擁有22 個π電子共振的芳香大環紫質。這些染料擁有合適的還原電位，高消光係數，良好的穩定性，以及高光電轉換效率。更重要的，其在可見光區段的吸光範圍廣泛，且其較低能量的Q band吸收位於在紅外光區段。基於上述條件，oxasmaragdyrins適合用來發展為太陽能光敏染料。我們亦於了oxasmaragdyrins 環上掛載了不同的推拉電子基，並進行研究與討論。令人意外的，掛載上tripheylamine為推電子基以及ethynylphenyl為共振鏈的染料其光電轉換效能相較於未修飾的染料並未增加。
    最後，我們合成了分別擁有一個和兩個羧基的新的二氮三硫 sapphyrins化合物並且將其應用於太陽能光敏染料。由電化學研究看來，其最低未佔軌域與二氧化鈦之傳導能帶間的差距太相近，使其不夠能讓激發的電子做有效的電子注入至二氧化鈦，故此染料的光電轉換效率不佳。
    至目前為止，此論文完成了單硫取代紫質最高的光電轉換效率，並且開發出了一系列新的大環紫質為高效率的太陽能光敏染料。

    This thesis reported the design and synthesis of novel core-modified and expanded porphyrin sensitizers for dye-sensitized solar cells. The development of these sensitizers starts off with novel thiaporphyrin and oxaporphyrin, which consists of ethynylphenyl group as a conjugated linker and carboxylic acid as anchoring group. Comparative photovoltaic studies of these heteroporphyrins with regular N4 porphyrins show that core-modification results in decreased performance, with moderate efficiency for thiaporphyrin and minute efficiency for oxaporphyrin. Following parts of this thesis regard the development strategy through core-modification. The periphery of thiaporphyrin was modified to obtain five more derivatives with A3B and A2B2 substitution pattern. The photophysical and electrochemical studies revealed that the π-extension through the ethynylphenyl group not only made the macrocycle planar but also increased their absorption bathochromicaly. Furthermore, substitution of the electron withdrawing cyano group produced higher polarizability required for the effective charge transfer from the porphyrin ring to the anchoring cyanoacrylic group. All these factors contributed to achieve the highest overall power conversion efficiency of 1.69% for N3S-ECN compared to other thiaporphyrin dyes.
    We also devote effort to uncover the potential of applying expanded porphyrins to DSSC studies. Boron chelated oxasmaragdyrins, a class of aromatic core-modified expanded porphyrin with a 22 π-electron conjugation were synthesized. These dyes provided desired redox potentials, high absorption coefficients, high stability, and higher power conversion efficiencies. More importantly, broad absorption spreading over the entire visible region and its lower energy Q bands covering part of the NIR region. The factor above made this class of compound an optimistic candidate for being one of the future selections of porphyrin-sensitized solar cells. The molecular engineering of these oxasmaragdyrins through peripheral substitution with various donors and acceptors was also discussed. To our surprise, utilizing of triphenylamine unit as a donor and ethynylphenyl group as a linker did not improve the overall performance for these dyes. Finally, novel mono or dual carboxylate functionalized N2S3 sapphyrins were prepared and applied as sensitizers in DSSCs for the first time. From the electrochemical studies it was observed that, the potential difference between the LUMO level of the dyes and conduction band of TiO2 was not sufficient for effective electron injection, which ultimately resulted in minute power conversion efficiencies for this class of dyes.
    In an effort to enhance the overall performance of porphyrin dyes, we also evaluated the co-sensitization effect. We combined two discretely moderate dyes, a free-base porphyrin and its zinc derivative, with complementary absorption spectra to construct a mixed porphyrin DSSC. From photo-action spectra, it is evident that the incident photon collection for the mixed dyes is higher than both the individual dyes due to the broader absorption. For the Mix-1, consisting of N4CA (2.71%) and N4ZnCA (3.09%), we observed conversion efficiency of 3.28% which higher than both the individual dyes, while for Mix-2, comprising for N4CN (1.94%) and N4ZnCN (3.52%), overall photon-to-current conversion efficiency of 4.18% was observed. We also evaluated the effectiveness of oxadiazole group as electron transporter. We attached an electron donor, oxadiazole ring and phenyl or thiophenephenyl group as linkers and carboxylic or cyanoacrylic group as anchor in D-π-A fashion to prepare three novel OD dyes. Although, the optical and electrochemical properties and DFT calculations confirmed good absorption features and effective charge separation, only moderate efficiency of 2.72% was observed for OD3 dye.
    So far, the work from this thesis has led to achieve the highest efficiency for thiaporphyrins and also unleashed a new class of porphyrinoids, the expanded porphyrins as highly efficient sensitizers for DSSCs.

    Abbreviations List of publications Abstract Ch 1. Introduction 1.1 Motivation 1 1.2 Natural photosynthesis 3 1.3 Basics of photovoltaics 5 1.4 Dye-sensitized solar cell 8 1.5 Sensitizers 13 1.5.1 Ruthenium sensitizers 13 1.5.2 Organic Dyes 15 1.5.3 Porphyrinoid sensitizers 16 1.5.3.1 Chlorins and Bacteriochlorins 17 1.5.3.2 Porphyrins 18 1.5.3.3 Corroles 33 1.5.3.4 Phthalocyanines and Subphthalocyanines 33 1.5.3.5 Core-modified Porphyrins 35 1.6 Scope of thesis 36 1.7 References 37 Section I: Core-modified porphyrins Ch 2. Effects of core-modification on porphyrin sensitizers to the efficiency of dye-sensitized solar cells 2.1 Introduction 46 2.2 Results and Discussion 48 2.2.1 Syntheses 48 2.2.2 Optical Spectroscopy 49 2.2.3 Cyclic Voltammetry 52 2.2.4 DFT and TD-DFT calculations 53 2.2.5 Dye loading experiments 55 2.2.6 Photovoltaic measurements 56 2.2.7 TCSPC measurements 57 2.3 Conclusions 59 2.4 Experimental Section 60 2.5 References 67 Ch 3. Synthesis of carboxylate functionalized A3B and A2B2 thiaporphyrins and their application in DSSCs 3.1 Introduction 69 3.2 Results and Discussion 70 3.2.1 Syntheses 70 3.2.2 Optical Spectroscopy 72 3.2.3 Electrochemical Spectroscopy 74 3.2.4 DFT and TD-DFT calculations 76 3.2.5 ATR-FTIR measurements 77 3.2.6 Dye loading experiments 79 3.2.7 Photovoltaic measurements 80 3.2.8 Electrochemical Impedance Spectroscopy 82 3.3 Conclusions 83 3.4 Experimental Section 84 3.5 References 93 Section II: Core-modified expanded porphyrins Ch 4. Novel expanded porphyrin sensitized solar cell using boryl oxasmaragdyrins as the sensitizers 4.1 Introduction 94 4.2 Results and Discussion 96 4.2.1 Syntheses 96 4.2.2 Optical Spectroscopy 97 4.2.3 CV Studies 100 4.2.4 DFT and TD-DFT calculations 102 4.2.5 Dye loading experiments 104 4.2.6 Photovoltaic measurements 105 4.2.7 Transient photoelectric and Charge-Extraction Measurements 106 4.2.8 Femtosecond transient absorption studies 108 4.3 Conclusions 109 4.4 Experimental section 111 4.5 References 119 Ch 5. Molecular engineering of boryl oxasmaragdyrin sensitizers through peripheral substituents: Effect of number and position of donor-acceptor groups 5.1 Introduction 121 5.2 Results and Discussion 122 5.2.1 Syntheses 122 5.2.2 Optical Spectroscopy 125 5.2.3 Electrochemical Spectroscopy 128 5.2.4 DFT and TD-DFT calculations 130 5.2.5 Dye loading measurements 133 5.2.6 Photovoltaic measurements 134 5.3 Conclusions 137 5.4 Experimental Section 138 Ch 6. Novel carboxylate functionalized N2S3 Sapphyrins: Synthesis, Photophysical and Photovoltaic properties 6.1 Introduction 158 6.2 Results and Discussion 160 6.2.1 Syntheses 160 6.2.2 Optical properties 162 6.2.3 Electrochemical properties 163 6.2.4 DFT calculations 164 6.2.5 Photovoltaic measurements 166 6.2.6 Electrochemical Impedance Spectroscopy 167 6.3 Conclusions 168 6.4 Experimental Section 169 6.5 References 175 Section III: Miscellaneous dyes Ch 7. Co-sensitization of free-base and zinc porphyrins: An effective strategy to improve the photon to current conversion efficiency of DSSCs 7.1 Introduction 177 7.2 Results and Discussion 179 7.2.1 Syntheses 179 7.2.2 Optical Spectroscopy 180 7.2.3 Electrochemical Spectroscopy 182 7.2.4 DFT and TD-DFT calculations 184 7.2.5 Dye loading measurements 187 7.2.6 Photovoltaic measurements 187 7.3 Conclusions 190 7.4 Experimental Section 191 7.5 References 196 Ch 8. Novel D-π-A type organic dyes with oxadiazole ring as electron transporter for DSSC application 8.1 Introduction 198 8.2 Results and Discussion 199 8.2.1 Syntheses 199 8.2.2 Optical Spectroscopy 200 8.2.3 Electrochemical Spectroscopy 201 8.2.4 DFT and TD-DFT calculations 202 8.2.5 Photovoltaic measurements 204 8.2.6 Electrochemical Impedance Spectroscopy 205 8.3 Conclusions 206 8.4 Experimental Section 207 8.5 References 211 Ch 9. Concluding Remarks 213 Appendix 1 Publications 216

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