Thiocyanate-Free Cycloruthenated Sensitizers for Dye-Sensitized Solar Cells

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阮帝暉(Nguyen The Duy) 查詢紙本館藏

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化學學系

論文名稱

Thiocyanate-Free Cycloruthenated Sensitizers for Dye-Sensitized Solar Cells
(Thiocyanate-Free Cycloruthenated Sensitizers for Dye-Sensitized Solar Cells)

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摘要(中)

本篇DUY1 ~ DUY6 敏化劑的CF3 基團在間位較鄰位有更有利的beta-LUSO 分布，讓電解質中的碘離子可以更有效將染料還原再生;DUY24-O, DUY24 和DUY24-Se 染料分子具有軟硫性，因此元件的光伏表現具有高的開路電壓；DUY24 ~ DUY29 與含有2-噻吩基吡啶環釕化配位基的NC103 做比較，元件的光電轉換效率最大可以提高達65%.

摘要(英)

This work described the synthesis and dye-sensitized solar cell (DSC) applications of fourteen thiocyanate-free complexes (DUY1 ~ DUY6, DUY24-O, DUY24-Se, DUY24 ~ DUY29) containing six- or five-membered rings as cyclometalated segments. The study of DUY1 ~ DUY6 showed that the sensitizers containing meta-CF3 group reveal a more favorable distribution of beta-lowest unoccupied spin orbital (beta-LUSO) for the stronger interaction with the reductant (iodide ion) in the electrolyte which promotes the dye regeneration compared to ortho-CF3. The
photovoltaic performances of DUY24-O, DUY24, and DUY24-Se sensitized cells showed that a higher VOC was obtained when a softer chalcogen is present in the dye molecule. DUY24 ~ DUY29-based cells showed up-to-65% higher efficiencies than the cell based on reported sensitizers containing 2-thienylpyridine cycloruthenated ligands (NC103 dye).

關鍵字(中)

★ beta-LUSO

關鍵字(英)

★ beta-LUSO

論文目次

Abstract .......................................................................................................................i
Acknowledgements ...................................................................................................iii
Dedication ..................................................................................................................v
Table of Contents ......................................................................................................vi
List of Tables.............................................................................................................ix
List of Figures ...........................................................................................................xi
List of Schemes .......................................................................................................xvi
List of Symbols and Abbreviations........................................................................xvii
List of Ligands and Target Complexes ...................................................................xxi
Chapter One: Introduction..........................................................................................1
1.1. Background ..................................................................................................1
1.2. Construction of dye-sensitized solar cells....................................................2
1.2.1. TCO substrate.....................................................................................2
1.2.2. TiO2 nanoparticle................................................................................3
1.2.3. Sensitizer ............................................................................................3
1.2.4. Electrolyte...........................................................................................5
1.2.5. Counter electrode................................................................................5
1.2.6. Sealing materials ................................................................................6
1.3. Operation principle of dye-sensitized solar cells .........................................6
1.4. Photovoltaic parameters ...............................................................................8
1.5. Main electron-transfer processes................................................................10
1.5.1. Electron-injection from the sensitizer to the TiO2 conduction band 10
1.5.2. Electron-transport in the TiO2 electrode ..........................................11
1.5.3. Dye-regeneration ..............................................................................12
1.5.4. Charge-recombinations ....................................................................13
1.6. Thiocyanate ruthenium sensitizers.............................................................14
1.7. Cyclometalation and thiocyanate-free cycloruthenated sensitizers ...........15
1.8. Dissertation objectives ...............................................................................21
Chapter Two: Results and Discussion .....................................................................23
2.1. Syntheses and characterizations of the cycloruthenated sensitizers ..........23
2.2. Optical properties .......................................................................................37
2.3. Electrochemical properties.........................................................................44
2.4. Density functional theory (DFT) calculations............................................48
2.4.1. The first ten DFT-calculated frontier orbitals distribution of
DUY-sensitizers .........................................................................................48
2.4.2. Time dependent density functional theory calculations...................57
2.4.3. Calculated -LUSO distribution on the oxidized forms of
DUY-sensitizers .........................................................................................70
2.5. Photovoltaic performance ..........................................................................74
2.5.1. Photovoltaic performance of DUY1−DUY6 sensitizers..................74
2.5.2. Photovoltaic performance of DUY24-O, DUY24, DUY24-Se
sensitizers....................................................................................................80
2.5.3. Photovoltaic performance of DUY24−DUY27 sensitizers..............84
2.5.4. Photovoltaic performance of DUY28 and DUY29 sensitizers ........88
Chapter Three: Conclusion ......................................................................................92
Chapter Four: Experimental Section........................................................................95
4.1. Preparation of sensitizers ...........................................................................95
4.1.1. Preparation of cycloruthenated six-membered-ring-based sensitizers
(DUY1−DUY6)..........................................................................................95
4.1.2. Preparation of cycloruthenated five-membered-ring-based sensitizers
(DUY24-O, DUY24-Se, and DUY24−DUY29)......................................110
4.2. Physicochemical studies...........................................................................134
4.3. DFT calculations ......................................................................................135
4.4. Device fabrication and characterization...................................................136
References ..............................................................................................................138

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指導教授

吳春桂(Chun-Guey Wu)

審核日期

2018-10-4

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