染料敏化太陽能電池具有成本低廉、容易製作、以及可撓性等多項優點，國內外已有許多團隊投入研究。染料敏化太陽能電池主要結構為透明導電基板、二氧化鈦層、染料層、電解質層及白金對電極層。由於傳統使用的染料N719為釕（Ru）金屬錯合物，內部含有重金屬容易對環境造成汙染，因此設計了新穎的有機染料期望可以取而代之，而白金貴金屬價格昂貴所以本實驗亦針對對電極進行研究，合成兩種低成本奈米複合材料，期望可以取代白金，降低製作的成本，並提升元件效率。

本研究共有四個部分，第一部分為介紹太陽能電池的沿革發展以及DSSC元件的製作流程及原理，第二部分為使用新穎有機染料並將其製備成染料液後再加以混合，形成混合染料溶液，可提供吸光互補、增加電子注入TiO2的通道等優點，再將其製成DSSC電池元件，並進行元件特性、阻抗頻譜、外部量子效率等分析。第三部分為使用GO-trimer複合材料結合Poly(o-methoxyaniline)，POMA高分子導電聚合物，製成新型的高導電性奈米複合材料後並進行表面形貌、結構組成以及電化學特性等分析，最終應用於DSSC元件的對電極上，並進行元件特性分析，結果顯示POMA/0.75% GO-trimer效率最高達到7.91%，高於白金的7.86%，證明是足以取代白金的新材料。第四部分為使用Ni/GO過度金屬大環錯合物經不同溫度燒結後再結合PEDOT:PSS導電高分子聚合物，製成新型奈米複合材料並進行表面形貌、結構組成以及電化學特性等分析，最終應用於DSSC元件的對電極上，並進行元件特性分析，結果顯示PEDOT-Ni/GO-300轉換效率高達8.44%，高於白金的7.86%，證明是足以取代白金的新材料。

Dye-sensitized solar cells (DSSCs) have many advantages such as low cost, easy fabrication, and flexibility; hence, they have attracted the attention of scholars. Typical components of a DSSC include TiO2 working electrodes, dye, electrolyte, and platinum (Pt) counter electrodes (CEs). Ruthenium-based sensitizers, such as N3 and N719 dyes, have achieved remarkable power conversion efficiency. However, the rarity and high cost of the ruthenium metal may limit their development for large-scale applications. Consequently, many researchers have focused on developing metal-free organic sensitizers. In addition, although Pt is commonly used for the CE, its high cost increases the price of DSSCs, which inhibits their commercialization and mass production, prompting researchers to actively search for cheaper electrode materials that can replace Pt and improve the efficiency of DSSCs.

This thesis includes four parts. First, the history and theory of the DSSCs and the experimental methods of this research were introduced. Second, two organic dyes were mixed and investigated for DSSC. The J-V curves, IPCE curves, and the EIS of device performance parameters of DSSCs based on the mixed organic dyes were analyzed.
Third, nanocomposite materials of GO-trimer and POMA were prepared. The electrode properties and device efficiency were analyzed. The DSSCs fabricated with the POMA/0.75% GO-trimer CEs achieved a power conversion efficiency of 7.91 %, which was higher than that of the Pt counter electrode. Fourth, nanocomposite materials of Ni/GO and PEDOT:PSS were prepared. The electrode properties and device efficiency were analyzed. The DSSCs fabricated with the PEDOT-Ni/GO-300 CEs achieved a power conversion efficiency of 8.44 %, which was higher than that of the Pt counter electrode.

致謝 III
摘要 V
Abstract VII
目錄 IX
圖目錄 XIII
表目錄 XVII
第一章 序論 1
1.1.1能源現況 1
1.1.2太陽能 2
1.2太陽能電池種類與發展 4
1.2.1染料敏化太陽能電池 5
1.3實驗儀器及研究原理 7
電化學分析儀(EIS) 10
外部量子轉換效率分析儀(IPCE) 11
紫外可見光光譜儀(UV-Visible Spectrophotometer) 12
電化學工作站 (IMPS、IMVS) 16
原子力顯微鏡(Atomic force microscopy，AFM) 18
掃描式場發射電子顯微鏡(Field emission scanning electron microscope，FE-SEM) 19
能量散佈光譜儀 ( Energy dispersive spectrometers，EDS) 19
X-光繞射(X-ray diffraction，XRD) 20
X光光電子能譜儀(x-ray photoelectron spectrometer，XPS) 20
傅立葉紅外線光譜儀(Fourier Transform Infrared Spectrometer，FTIR) 21
拉曼光譜分析儀（Raman） 21
1.4參考文獻 22
第二章 混合各式體積比例之有機染料應用於染料敏化太陽能電池 25
2.1 前言 25
2.1.1新穎染料之設計背景及混合動機 27
2.2實驗方法 28
2.2.1有機染料配置及混成 28
2.2.2工作電極製備 28
2.2.3對電極製備 29
2.2.4染料敏化太陽能電池元件製作 29
2.3結果與討論 30
2.4結論 37
2.5參考文獻 38
第三章 聚鄰甲氧基苯胺-氧化石墨烯還原三苯胺奈米複合材料應用於染料敏化太陽能電池對電極之研究 39
3.1前言 39
3.2實驗方法 40
3.2.1材料製備(輔大林筱媛提供) 40
3.2.2工作電極製備 42
3.2.3對電極製備 42
3.2.4染料敏化太陽能電池元件製作 42
3.3結果與討論 43
3.3.1表面形貌分析 43
3.3.2材料組成分析 46
3.3.3電化學特性分析 51
3.3.4元件特性分析 52
3.4結論 56
3.5參考文獻 58
第四章 聚二氧乙基噻吩-聚苯乙烯磺酸結合不同燒結溫度之石墨烯混摻鎳大環錯合物之研究 59
4.1前言 59
4.2實驗方法 60
4.2.1材料製備(輔大周育如提供) 60
4.2.2工作電極製備 62
4.2.3對電極製備 63
4.2.4染料敏化太陽能電池元件製作 63
4.3結果與討論 64
4.3.1表面形貌分析 64
4.3.2材料組成分析 68
4.3.3電化學特性分析 74
4.3.4元件特性分析 75
4.4結論 79
4.5參考文獻 81
第五章 總結論 83

1.4參考文獻
[1] The BP Statistical Review of World Energy-oil (2016)
[2] The BP Statistical Review of World Energy-Natural gas (2016)
[3] The BP Statistical Review of World Energy-Coal (2016)
[4] GORE, Al. An inconvenient truth: The planetary emergency of global warming and what we can do about it. Rodale, 2006.
[5] https://zh.wikipedia.org/wiki/核能發電對環境的衝擊
[6]BP Statistical Review of World Energy-Energy Outlook(2018)
[7] [8] 郭浩中，《太陽能光電技術》，(台灣:五南圖書出版，2012)
[9] A. Guechi ; M. Chegaar ; M. Ailleriec,”Air Mass Effect on the Performance
of Organic Solar Cells.” Energy Procedia, 2013, 714–721
[10] 莊秉元，〈染料敏化太陽能電池元件結構及材料特性之研究〉，(國立東華大學光電工程研究所碩士論文，2012)，1-19。
[11]https://zh.wikipedia.org/wiki/File:Solar_Spectrum.png
[12]https://commons.wikimedia.org/wiki/File:PVeff(rev171030).jpg
[13]M. K. Nazeeruddin, P. Pechy, and M. Gratzel, Chem. Commun (1997) 1705
[14] Nazeeruddin, Md K., P. Pechy, and M. Grätzel. "Efficient panchromatic sensitization of nanocrystalline TiO 2 films by a black dye based on a trithiocyanato–ruthenium complex." Chemical Communications 18 (1997): 1705-1706..
[15] M. Grätzel et al, “A Low-Cost, High-Efficiency Solar Cell Based on Dye-Sensitized Colloidal TiO2 Films”, Nature, 1991
[16] Yella, Aswani, et al. "Porphyrin-sensitized solar cells with cobalt (II/III)–based redox electrolyte exceed 12 percent efficiency." science 334.6056 (2011): 629-634.
[17] Chih-Hung, Tsai, et al. "Influences of textures in fluorine-doped tin oxide on characteristics of dye-sensitized solar cells." Organic Electronics 12.12 (2011): 2003-2011.
[18]A. Hagfeldt, M. Grätzel, Chem. Rev. 95 (1995) 49
[19] O'regan, Brian, and Michael Grätzel. "A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films." nature 353.6346 (1991): 737-740.
[20] Nazeeruddin, Mohammad K., et al. "Engineering of efficient panchromatic sensitizers for nanocrystalline TiO2-based solar cells." Journal of the American Chemical Society 123.8 (2001): 1613-1624.
[21] W. Shockley , H. J. Queisser , j. Appl. Phys. 32 (1961) 510.
[22] R. P. Wijesundera , M. Hidaka , K. Koga , M. Sakai , W. Siripala ,Thin Solid Films 500 (2006) 241.
[23] K. Tennakone , A.R. Kumarsinghe, P.M. Sirimanne ,JJournal of Photochemistry and Photobiology A : Chemistry 88 (1995) 39.
[24] C. Y. Lin ,Y. H. Lai , D. Mersch and E.Reisne , Chem. Sci. , 3(2012)3482.

2.5參考文獻
[1] W. Zeng, Y. Cao, Y. Bai, Y. Wang, Y. Shi, M. Zhang, F. Wang, C. Pan,
P. Wang, Chem. Mater. 22 (2010) 1915.
[2] M. K. Nazeeruddin, R. Humphry-Baker, P. Liska, M. Grätzel﹐J.
Phys. Chem. B 107 (2003) 8981.
[3] A. Fumihiko, T. Tsukasa, J. Molecular Structure 658 (2003) 25.
[4] G. J. Meyer, J. Chem. Educ. 74 (1997) 652.
[5] A. Helena Greijer, L, Jan, H, Anders, Solar Energy 75 (2003) 169.
[6] M. Grätzel, J. Photochem. Photobio. A 164 (2004) 3.
[7] M. Adachi, M. Sakamoto, J. Jiu, Y. Ogata, S. Isoda, J. Phys. Chem. B
110 (2006) 13872.
[8] M. Grätzel, J. Photochem. Photobiol. A 168 (2004) 235.
[9] M. K. Nazeeruddin, A. Kay, L. Rodicio, R. Humphry-Baker, E.
Müller, P. Liska, N. Vlachopoulos, M. Grätzel, J. Am. Chem. Soc.
115 (1993) 6382.
[10] M. K. Nazeeruddin, P. Péchy, T. Renouard, S. M. Zakeeruddin, R.
Humphry-Baker, P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover,
L. Spiccia, G. B. Deacon, C. A. Bignozzi, M. Grätzel, J. Am. Chem.
Soc. 123 (2001) 1613.
[11] K. Hara, Kurashige, M., Ito, S., Shinpo, A., Suga, S., Sayama, K.,
Arakawa, H. Chem. Commun. (2003) 252.
[12]陳玉麟，〈應用新穎材料於染料敏化太陽能電池與電致變色元件之研究〉，(國立東華大學光電工程研究所碩士論文，2016)，79-84
[13]陳致翰，〈新型染料敏化太陽能電池結構及新穎有機染料之研究〉，(國立東華大學光電工程研究所碩士論文，2014)，45-47
 
3.5參考文獻
[1] Chiang, C. K_, et al. "Electrical conductivity in doped polyacetylene." Physical Review Letters 39.17 (1977): 1098.

[2] Potts, Jeffrey R., et al. "Graphene-based polymer nanocomposites." Polymer52.1 (2011): 5-25.
[3] http://cmnst.ncku.edu.tw/ezfiles/23/1023/img/2601/435955689.pdf
[4] Ashutosh Tiwari,Lokman Uzun,《Advanced Functional Materials》,Scrivener Publishing L.L.C. 2015
[5]Bhattacharya, Amit, and Amitabha De. "Conducting composites of polypyrrole and polyaniline a review." Progress in Solid State Chemistry 24.3 (1996): 141-181.
[6]Mortimer, Roger J. "Electrochromic materials." Chem. Soc. Rev. 26.3 (1997): 147-156..
[7] 黃偉智，〈奈米複合材料於染料敏化太陽能電池對電極之研究〉(國立東華大學工電工程研究所碩士論文，2015)。

4.5參考文獻
[1] Geim, A. K.; Novoselov, K. S., The rise of graphene. Nat Mater 2007, 6 (3), 183-191.
[2] Potts, Jeffrey R., et al. "Graphene-based polymer nanocomposites." Polymer52.1 (2011): 5-25
[3] Ramanathan, T.; Abdala, A. A.; Stankovich, S.; Dikin, D. A.; Herrera- Alonso, M.; Piner, R. D.; Adamson, D. H.; Schniepp, H. C.; Chen, X.; Ruoff, R. S.; Nguyen, S. T.; Aksay, I. A.; Prud'homme, R. K.; Brinson,L. C., Functionalized graphene sheets for polymer nanocomposites.Nat Nanotechnol 2008, 3 (6), 327-331.
[4] Wang, X.; Zhi, L. J.; Mullen, K., Transparent, conductive graphene electrodes for dye-sensitized solar cells. Nano Lett 2008, 8 (1), 323-327.
[5] Gong, Feng, et al. "NiSe 2 as an efficient electrocatalyst for a Pt-free counter electrode of dye-sensitized solar cells." Chemical Communications 49.14 (2013): 1437-1439.
[6]Dou, Y. Y., et al. "Nickel phosphide-embedded graphene as counter electrode for dye-sensitized solar cells." Physical Chemistry Chemical Physics 14.4 (2012): 1339-1342.
[7] Yeh, Min-Hsin, et al. "A low-cost counter electrode of ITO glass coated with a graphene/Nafion® composite film for use in dye-sensitized solar cells." Carbon50.11 (2012): 4192-4202.
[8] Muhammad Zubair,Maria Mustafa ,Adnan Ali ,Yang Hoi Doh ,Kyung Hyun Choi, et al. "Improvement of solution based conjugate polymer organic lightemitting diode by ZnO–graphene quantum dots. " J Mater Sci: Mater Electron (2015) 26:3344–3351
[9] 郭哲瑋，〈聚二氧乙基噻吩/石墨烯鎳金屬顆粒混成材料之製備及在電化學感測與透明導電膜之應用〉，(私立輔仁大學化學研究所碩士論文，2016)。
[10] Sheng Hsiung Chang, et al. "Unraveling the Enhanced Electrical Conductivity of PEDOT:PSS Thin Filmsfor ITO-Free Organic Photovoltaics" Research Center for New Generation Photovoltaics, National Central University,Jongli 32001, Taiwan. (2014)