本論文以多氟單體做為有機太陽能電池之緩衝層，藉由蒸鍍及旋轉塗佈兩種不同的方式成膜在ITO基板上，其中溶液製程以DCB取代THF後大幅改善了成膜的完整度。之後比較不同含氟數量的材料對於元件效率的影響。材料分析上，多氟單體有良好的熱穩定性及高達97%的可見光穿透度。由於材料為不導通的絕緣體，且材料與主動層溶劑會有微溶的現象，我們透過實驗提出了一個解釋論述：多氟單體在緩衝層中，載子並非直接經過材料的導通，而是材料微溶後的穿隧。之後也透過實驗及量測的數據解釋材料在塗完主動層後微溶的結果是：材料仍然完全覆蓋在ITO的表面，但等效厚度會因而改變，從而使得厚度符合穿隧的條件，且仍有平坦化ITO的效果。

本實驗中做到最佳的參數為:12F以DCB為溶劑旋轉塗佈製程作為陽極緩衝層，元件結構為:ITO/12F/P3HT:PCBM/LiF/Al。因為有著良好的平坦化效果、防止漏電流及透過材料的極性引導穿隧的原因，元件有著很高的FF值66.8%，功率轉換效率為2.34%，高過以PEDOT:PSS為緩衝層的基本元件2.20%。

In this thesis, multi-fluoro monomers were investigated as the buffer layer for the organic solar cells. In the analysis of materials, multi-fluoro monomers exhibited good thermal stability and high transmittance up to 97% in visible light region. Two methods have been tried to form the film on the ITO substrate, first one is thermal deposition and second one is spin coating. Through spin coating, it’s found that the completeness and quality of film was obviously improved by replacing the solvent THF with DCB. However, the multi-fluoro monomer are insulators and they will be dissolved to the solvent of activity layer, we assumed an explanation to make sure that the charge carriers inside the device will tunneling through it. According to our experiments and measurements, we also have proved that materials will remain covered completely on ITO substrate after spin coating active layer on it, but the residual thickness will be thickened. Furthermore, it still remains the effect to smooth the surface of ITO.

Under these research, the optimized method to form the film for anode buffer layer with multi-fluoro monomers is to dissolve 12F in DCB to spin coating. With the benefits of highly smoothing to the surface of ITO, avoiding leakage of current and inducing charge carries to tunneling with the more polarized materials, the device configurations based on the ITO/12F/P3HT:PCBM/LiF/Al. exhibit a fill factor of 66.8% and higher efficiency of 2.34% as compared to the devices fabricating by PEDOT:PSS.

誌謝 i
摘要 ii
Abstract iii
目錄 iv
圖目錄 vii
表目錄 ix
第一章 緒論 1
1.1前言 1
1.2有機太陽能電池結構發展 3
1.2.1單層結構有機太陽能電池 3
1.2.2雙層異質接面結構有機太陽能電池 4
1.2.3混合異質接面結構有機太陽能電池 5
1.3有機太陽能電池基本元件材料簡介 6
1.3.1電洞注入緩衝層(PEDOT:PSS) 6
1.3.2電荷施體材料(P3HT) 7
1.3.3電荷受體材料(PCBM) 8
1.3.4電子注入緩衝層(LiF) 9
1.4文獻回顧 10
1.5研究動機與目的 12
第二章 太陽能電池基本理論 13
2.1有機太陽能電池的轉移機制 13
2.2光電轉換原理 14
2.3等效電路 18
2.4 影響效率之重要因子 19
2.4.1開路電壓(Voc) 20
2.4.2短路電流(Isc) 20
2.4.3填充因子(FF) 21
第三章 實驗儀器及原理 24
3.1製程儀器 24
3.1.1超音波洗淨機(Ultrasonic Cleaners) 24
3.1.2紫外臭氧清洗機(UV Ozone) 25
3.1.3手套箱(Glove Box) 26
3.1.4旋轉塗佈機(Spin Coaters) 27
3.1.4蒸鍍機(Evaporator) 28
3.2分析儀器 29
3.2.1太陽光譜模擬器(Solar Simulator) 29
3.2.2可見光紫外光分光光譜儀 (UV/VIS Spectrophotometer) 30
3.2.3熱重分析儀(TGA) 31
3.2.4光電子光譜儀(Photoelectron Spectrometer，AC-2) 32
3.2.5橢偏儀(Ellipseometer) 32
3.2.6原子力顯微鏡(AFM) 33
第四章 實驗部分 35
4.1實驗架構 35
4.2實驗藥品 37
4.3實驗步驟 40
4.3.1配藥流程 40
4.3.2元件製程 41
第五章 結果與討論 44
5.1多氟單體熱穩定分析(TGA) 44
5.2多氟單體穿透度分析(UV-VIS) 45
5.3多氟單體載子傳輸能力分析 46
5.4 18F(蒸鍍)作為陰極緩衝層 47
5.5 18F(蒸鍍)作為陽極緩衝層 48
5.6 18F(蒸鍍)和其他電洞阻擋層 50
5.7 18F(旋轉塗佈，THF) 51
5.8 18F(旋轉塗佈，DCB) 53
5.9多氟系列比較(DCB) 54
5.10多氟單體溶解度測試(AFM) 56
第六章 結論 60
參考文獻 61

[1] U.S. Energy Information Administration, "International Energy Outlook" (2013)
[2] U.S. Energy Information Administration, "Monthly Energy Review March" (2015)
[3] Service R. "Outlook brightens for plastic solar cells.” Science. 15, April (2011) 293.
[4] Kearns, David, and Melvin Calvin. "The photovoltaic effect and photoconductivity in laminated organic systems." J. Chem. Phys. 29 (1958) UCRL—8441.
[5] Amal K. Ghosh1, Don L. Morel1, Tom Feng, Robert F. Shaw and Charles A. Rowe Jr. "Photovoltaic and rectification properties of Al/Mg phthalocyanine/Ag Schottky‐barrier cells." J. Appl. Phys. 45 (1974) 230.
[6] Tang, Ching W. "Two‐layer organic photovoltaic cell." Appl. Phys. Lett. 48 (1986) 183.
[7] Gunes, Serap, and Niyazi Serdar Sariciftci. "An overview of organic solar cells." Journal of Engineering and Natural Sciences. 25 (2007) 1.
[8] Winder, Christoph, and Niyazi Serdar Sariciftci. "Low bandgap polymers for photon harvesting in bulk heterojunction solar cells." J. Mater. Chem. 14 (2004): 1077.
[9] G Yu, J Gao, JC Hummelen, F Wudl, AJ Heeger. "Polymer photovoltaic cells: enhanced efficiencies via a network of internal donor-acceptor heterojunctions." Science. 270 (1995) 1789.
[10] Wang, Hsing-Ju, Chih-Ping Chen, and Ru-Jong Jeng. "Polythiophenes comprising conjugated pendants for polymer solar cells: a review." Materials. 7 (2014) 2411.
[11] Vosgueritchian, Michael, Darren J. Lipomi, and Zhenan Bao. "Highly conductive and transparent PEDOT: PSS films with a fluorosurfactant for stretchable and flexible transparent electrodes." Adv. Funct. Mater. 22 (2012) 421.
[12] Chang, Yi-Ming, Leeyih Wang, and Wei-Fang Su. "Polymer solar cells with poly (3, 4-ethylenedioxythiophene) as transparent anode." Organic Electronics. 9 (2008) 968.
[13] J. Huanga, P.F. Millerb, J.C. de Mellob, A.J. de Mellob, D.D.C. Bradley. "Influence of thermal treatment on the conductivity and morphology of PEDOT/PSS films." Synthetic Metals. 139 (2003) 569.
[14] Toshihiro Yamanari, Tetsuya Taima, Jun Sakai, Jun Tsukamoto and Yuji Yoshida. "Effect of buffer layers on stability of polymer-based organic solar cells." Jpn. J. Appl. Phys. 49 (2010) 01AC02.
[15] Fuzhi Wang, Gang Sun, Cong Li, Jiyan Liu, Siqian Hu, Hua Zheng, Zhan’ao Tan , and Yongfang Li. "Finding the Lost Open-Circuit Voltage in Polymer Solar Cells by UV-Ozone Treatment of the Nickel Acetate Anode Buffer Layer." ACS Appl. Mater. Interfaces. 6 (2014) 9458.
[16] Maher Al-Ibrahim, H.-Klaus Roth, M. Schroedner, Alexander Konkin, Uladzimir Zhokhavets, Gerhard Gobsch, Peter Scharff,and Steffi Sensfuss. "The influence of the optoelectronic properties of poly (3-alkylthiophenes) on the device parameters in flexible polymer solar cells." Organic Electronics 6 (2005) 65.
[17] Thompson, Barry C., and Jean MJ Frechet. "Polymer–fullerene composite solar cells." Angew. Chem. Int. Ed. 47 (2008) 58.
[18] Dang, Minh Trung, Lionel Hirsch, and Guillaume Wantz. "P3HT: PCBM, best seller in polymer photovoltaic research." Adv. Mater. 23 (2011) 3597.
[19] C. H. Lee, G. Yu, D. Moses, K. Pakbaz, C. Zhang, N. S. Sariciftci, A. J. Heeger, and F. Wudl. "Sensitization of the photoconductivity of conducting polymers by C 60: Photoinduced electron transfer." Phys. Rev. B. 48 (1993) 15425.
[20] S. K. M. Jönsson, E. Carlegrim, F. Zhang1, W. R. Salaneck1 and M. Fahlman. "Photoelectron spectroscopy of the contact between the cathode and the active layers in plastic solar cells: the role of LiF." Jpn. J. Appl. Phys. 44 (2005) 3695.
[21] Christoph J. Brabec, Sean E. Shaheen, Christoph Winder, N. Serdar Sariciftci and Patrick Denk. "Effect of LiF/metal electrodes on the performance of plastic solar cells." Appl. Phys. Lett. 80 (2002) 1288.
[22] Riccardo Po, Chiara Carbonera, Andrea Bernardi and Nadia Camaioni "The role of buffer layers in polymer solar cells." Energy Environ. Sci. 4 (2011) 285.
[23] Jin Young Kim, Sun Hee Kim, Hyun-Ho Lee, Kwanghee Lee, Wanli Ma, Xiong Gong and Alan J. Heeger. "New architecture for high-efficiency polymer photovoltaic cells using solution-based titanium oxide as an optical spacer." Adv. Mater. 18 (2006) 572.
[24] Kang, Bonan, L. W. Tan, and S. R. P. Silva. "Fluoropolymer indium-tin-oxide buffer layers for improved power conversion in organic photovoltaics." Appl. Phys. Lett. 93 (2008) 133302.
[25] Vishal Shrotriya, Gang Li, Yan Yao, Chih-Wei Chu, and Yang Yang "Transition metal oxides as the buffer layer for polymer photovoltaic cells." Appl. Phys. Lett. 88 (2006) 073508.
[26] Paul W. M. Blom, Valentin D. Mihailetchi, L. Jan Anton Koster, and Denis E. Markov. "Device physics of polymer: fullerene bulk heterojunction solar cells." Adv. Mater. 19 (2007) 1551.
[27] Bharathan, Jayesh M., and Yang Yang. "Polymer/metal interfaces and the performance of polymer light-emitting diodes." J. Appl. Phys. 84 (1998) 3207.
[28] Qi Xu, Fuzhi Wang, Zhan’ao Tan,, Liangjie Li, Shusheng Li, Xuliang Hou, Gang Sun, Xiaohe Tu, Jianhui Hou, and Yongfang Li. "High-Performance Polymer Solar Cells with Solution-Processed and Environmentally Friendly CuO x Anode Buffer Layer." ACS Appl. Mater. Interfaces. 5 (2013) 10658.
[29] 陳盛煒，「光伏薄膜混摻Alq3的研究」，中山大學碩士論文(2005).
[30] Peumans, Peter, and Stephen R. Forrest. "Separation of geminate charge-pairs at donor–acceptor interfaces in disordered solids." Chem. Phys. Lett. 398 (2004) 27.
[31] C. Y. Kuo, W. C. Tang, C. Gau, T. F. Guo, and D. Z. Jeng. "Ordered bulk heterojunction solar cells with vertically aligned TiO2 nanorods embedded in a conjugated polymer." Appl. Phys. Lett.93 (2008) 33307.
[32] S. M. Sze Physics of semiconductor devices, 2ntl Edition. Editor John Wiley & Sons, New York. (1981).
[33] Bernede, J. C. "Organic photovoltaic cells: history, principle and techniques." J. Chil. Chem. Soc. 53 (2008) 1549.
[34] Hoppe, Harald, and Niyazi Serdar Sariciftci. "Organic solar cells: An overview." J. Mater. Res. 19 (2004) 1924.
[35] Markus C. Scharber,* David Mühlbacher, Markus Koppe, Patrick Denk, Christoph Waldauf,Alan J. Heeger, and Christoph J. Brabec. "Design rules for donors in bulk-heterojunction solar cells-towards 10% energy-conversion efficiency." Adv. Mater.18 (2006) 789.
[36] Rand, Barry P., Diana P. Burk, and Stephen R. Forrest. "Offset energies at organic semiconductor heterojunctions and their influence on the open-circuit voltage of thin-film solar cells." Phys. Rev. B 75 (2007) 115327.
[37] C. M. Ramsdale1, J. A. Barker1, A. C. Arias1, J. D. MacKenzie1, R. H. Friend1 and N. C. Greenham. "The origin of the open-circuit voltage in polyfluorene-based photovoltaic devices." J. Appl. Phys. 92 (2002) 4266.
[38] Christoph J. Brabec, Antonio Cravino, Dieter Meissner, N. Serdar Sariciftci, Thomas Fromherz, Minze T. Rispens, Luis Sanchez, and Jan C. Hummelen. "Origin of the open circuit voltage of plastic solar cells." Adv. Funct. Mater. 11 (2001) 374.
[39] Ruifeng He, Lei Yu , Ping Cai, Feng Peng, Jin Xu, Lei Ying, Junwu Chen, Wei Yang, and Yong Cao. "Narrow-band-gap conjugated polymers based on 2, 7-dioctyl-substituted dibenzo [a, c] phenazine derivatives for polymer solar cells." Macromolecules. 47.9 (2014) 2921.
[40] T Yamanari, T Taima, J Sakai, K Saito. "Origin of the open-circuit voltage of organic thin-film solar cells based on conjugated polymers." Solar Energy Materials and Solar Cells 93 (2009) 759.
[41] Padinger, Franz, Roman S. Rittberger, and Niyazi S. Sariciftci. "Effects of postproduction treatment on plastic solar cells." Adv. Funct. Mater. 13 (2003) 85.
[42] Dhritiman Gupta, Sabyasachi Mukhopadhyay, K.S. Narayan. "Fill factor in organic solar cells." Solar Energy Materials & Solar Cells. 94 (2010) 1309.
[43] 宋慶軍，熊卓，「太陽能電池串聯和並聯電阻問題的探討」，昆山科技大學研究報告(2011)
[44] Kim, Myung-Su, Bong-Gi Kim, and Jinsang Kim. "Effective variables to control the fill factor of organic photovoltaic cells." ACS Appl. Mater. Interfaces. 1 (2009) 1264.
[45] Gupta, Dhritiman, Monojit Bag, and K. S. Narayan. "Correlating reduced fill factor in polymer solar cells to contact effects." Appl. Phys. Lett. 92 (2008) 093301.
[46] ThreeBond Lt. "Three Bond Technical News Issued" March 20, (1987)
[47] Ossila Ltd. "Spin Coating: A Guide to Theory and Techniques"
[48] Villalva, Marcelo Gradella, and Jonas Rafael Gazoli. "Comprehensive approach to modeling and simulation of photovoltaic arrays." IEEE Transactions on Power Electronics 24 (2009) 1198.
[49] Coats, A. W., and J. P. Redfern. "Thermogravimetric analysis. A review. "Analyst. 88 (1963) 906.
[50] 陳金鑫，黃孝文，「有機電激發光材料與元件」，五南(2005)
[51] 龎俊傑，「含氟碳氫離子性高分子應用於燃料電池質子交換膜之研究」，中山大學碩士論文(2013).
[52] 徐以芸，「探討三氟甲基數目對於磺酸化聚芳香高分子薄膜特性之影響」，中山大學碩士論文(2015).
[53] BR Liaw, WY Huang, PT Huang, MY Chang, and YK Han. "Novel poly (arylene ether) s containing multi-substituted pentaphenylene moiety." Polymer. 48 (2007) 7087.