臺灣博碩士論文加值系統

近年來，經濟快速發展導致能源大量消耗。為解決經濟發展所帶來的能源危機等問題，各國都在積極尋找替代能源。目前已開發的替代性能源中，最受到各界廣泛重視的，莫過於是具有安全性高、無污染、無噪音特性的太陽能電池。目前在商業上量產的太陽能電池以矽(silicon)為主要材料。雖然這類太陽能電池的能量轉換效率可高達30%，但是其原料價格較為昂貴，因此製作成本較高。因此，多種有機太陽能電池已陸續被開發出來。
有機或高分子太陽能電池相對其他種類太陽能電池具有輕薄、大面積、可撓曲、低製作成本、高吸光之優點。高分子太陽能電池中，以Poly(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) 為主動層者具有高達 5 ~ 6 %的效率，而廣受重視。
本論文主要探討在主動層P3HT中添加自製碳奈米點以取代PCBM 所製備元件之光電轉換效率。自製碳奈米點價格約為PCBM的萬分之一，若能發揮接近後者之效能，則可大幅降低元件之價格。碳奈米點原為水溶性，經由表面改質後，發現能順利分散於有機溶劑DCB中。然而，目前測得之光電轉換效率只有0.005，遠低於對照組。未來將繼續縮小碳奈米點之尺寸與提昇表面修飾物之電荷傳導度。

In the past few years, the rapid development of worldeconomy leads to energy crisis. Every country started to search for alternative energy sources because of the demanding energy consumption. So far, the highly valued renewable energy source is the solar energy, which is safe, pollution-free, and noiseless. Currently, the solar cellsfor practicaluses are mainly silicon-based. Although their conversion efficiency can reach as high as 30%, the manufacturing cost is too high. Therefore, several organic photovoltaic cells have been developed.
Compared toother types of solar cell, polymer solar cells have been widely noted due to their advantages including easy fabrication, low cost, light weight, large area, shape flexibility, , and high optical absorption. Among the polymer solar cells, thosewithpoly (3-hexylthiophene) (P3HT)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) blends as the active layer show high energy conversion efficiency.
This thesis studied the IPEC (Incident photon to electron conversion efficiency)of the devices using the carbon nanodots to replace the PCBM in the active layer of P3HT.Since the price of the home-made carbon nanodots is about one ten-thousandth that of the PCBM, a large reduction of the device cost is expected if the carbon nanodots function like PCBM. The water soluble carbon nanodots were found to disperse in the organic solvent of DCB after surface modification. However, the measured conversion efficiency of the devices isonly 0.005 at present, much lower than that of the benchmark device.The carbon nanodots are kept being shrunk in size and the surface modifiers, enhanced in electrical conductance.

致謝
摘要 I
Abstract III
目錄 V
圖目錄 VIII
表目錄 XII
第一章 緒論 1
1.1前言 1
1.2太陽能電池的發展史 5
1.3太陽能電池的定義與種類 12
1.4碳奈米點之介紹 18
1.5研究動機 20
第二章 實驗相關理論 21
2.1能帶理論 21
2.2共軛高分子的介紹 25
2.3共軛高分子導電原理 30
2.4光激發螢光原理 34
2.5 導電高分子PEDOT and PEDOT:PSS 36
2.6 有機高分子太陽能電池 38
2.6.1 電子傳輸層 39
2.6.2 電洞傳輸層 39
2.7 有機太陽能電池發電原理 41
2.7.1 光激發和激子生成 41
2.7.2 激子擴散 42
2.7.3 激子分離 42
2.7.4 電荷傳輸和電荷收集 42
2.8太陽能電池元件數據量測 44
2.8.1 開路電壓(Voc) 45
2.8.2 短路電流(Isc) 45
2.8.3 填充因子(FF) 47
2.8.4 光電轉換效率(Photovoltaic Conversion Efficiency) 48
2.8.5電流-電壓(J-V)特性曲線 49
第三章 實驗部分 54
3.1 實驗藥品 54
3.2 實驗儀器 55
3.3 迴流法製備碳球 56
3.3.1 未加硫酸製程 56
3.3.2 加硫酸製程 57
3.4 OPV元件製作流程 58
3.4.1 元件製作流程 58
3.4.2 元件結構 59
3.4.3 ITO清洗與蝕刻 59
3.4.4 電洞傳輸層製備 60
3.4.5 主動層製備 61
3.4.6 陰極蒸鍍 62
第四章 結果與討論 65
4.1碳奈米點之表面改質 65
4.2碳奈米點粒徑 70
4.3碳奈米點 FTIR 吸收光譜 71
4.4碳奈米點溶液光激發光(PL) 72
4.5有機高分子太陽能電池(OPV)量測 77
結論 86
參考文獻 88

1.Organization of Petroleum Exportion Countries,OPEC
http://www.opec.org/home/basket.aspx
2.梁國淦. 染料敏化太陽能電池中之超快光致電子轉移過程.
3. Becquerel, E. Acad. Sci.1839, 9, 145.
4. Green, M. A. Proceeding of the 21st IEEE Photovoltaic Specialists Conference., Orlando, USA: IEEE Publication, 1990.
5. Chapin, D. M.; Fuller, C. S.; Pearson, G. L., A New Silicon pn Junction
Photocell for Converting Solar Radiation into Electrical Power., J. Appl. Phys.,
25 (1954) 676.
6. 王抒揚，肖藝能，劉吉，孫銘澤. 有機太陽能電池的原理和應用.
7. Carlson, D. E.; Wronski, C. R., Amorphous Silicon Solar Cell. Appl. Phy.
Lett., 28 (1976) 671-673.
8. Benagli, S.; Borrello, D.; Vallat-Sauvain E., High-efficiency amorphous
silicon devices on LPCVD-ZnO TCO prepared in industrial KAI TM-M R &;
D reactor., In Proceedings of the 24th European Photovoltaic Solar Energy
Conference, (2009) 2293.
9. Repins, I.; Contreras, M.; Romero, M.; Yan, Y.; Metzger, W.; Li, J.; Johnston, S.; Egaas, B.; DeHart, C.; Scharf, J., Characterization of 19.9%-efficienct CIGS
absorbers. IEEE Photovoltaics Specialists Conference Record, May 11-16,
2008.
10. Xuanzhi, Wu., High-efficiency polycrystalline CdTe thin-film solar cells Solar Energy, 77, 2004, 803-814.
11. Ghosh, A. K.; Feng, T. J. Appl, Phys 1978, 49, 5982.
12. Tang, C. W. Appl. Phys. Lett. 1986, 48, 183
13. Sariciftci, N. S.; Smilowitz, L.; Heeger, A. J.; Wudl, F. Science 1992, 258, 1474.
14. Sariciftci, N. S.; Braun, D.; Zhang, C.; Srdanov, V. I.; Heeger,
A. J.; Stucky, G.; Wudl, F. Appl. Phys. Lett. 1993, 62, 585.
15. Yu, G.; Gao, J.; Hummelen, J.; Wudl, F.; Heeger, A. J.Science 1995, 270, 1789.
16. Shaheen, S. E.; Brabec, C. J.; Sariciftci, N. S.; Padinger, F.;Fromherz, T.; Hummelen, J. C. Appl. Phys. Lett. 2001, 78,841.
17. Padinger, F.; Rittberger, R. S.; Sariciftci, N. S. Adv. Funct. Mater. 2003, 13, 85.
18. Li, G.; Shortriya, V.; Yao, Y.; Yang, Y. J. Appl. Phys. 2005, 98, 043704
19. Ma, W.; Yang, C.; Gong, X.; Lee, K.; Heeger, A. J. Adv. Funct. Mater. 2005, 15, 1617.
20. Wen-Hao Chen; J-HP; Y-MC. Conjugated Polymer-based Solar Cells.67:61-6.
21. 郭明村,. 薄膜太陽能電池發展近況. 工業材料雜誌 2003, 203, 138.
22. Hurd, F.; Livingston, R. J. Phys. Chem.1940, 44, 865.
23. (a) Oster, G.; Bellin, J. S.; Kinball, R. W.; Scharder, M. E. J. Am. Chem. Soc.1959, 81,5095. (b) Chaberek, S.; Shepp, A.; Allen, R. J. J., Phys. Chem.1965, 69, 641. (c) Kearns, D.R.; Hollins, R. A.; Khan, A. U.; Chambers, R. W.; Radlick, P. J. Am. Chem. Soc.1967, 89,5455.
24. Gerischer, H.; Tributsch, H. Ber., Bunsenges. Phys. Chem.1968, 72, 437.
25. Regan, B. O.; Grätzel, M., Nature 1991, 343, 737.
26. Moore, G. F.; Brudvig, G. W., Annu. Rev. Condens. Matter Phys. 2011, 2, 303.
27. Williams, R. J., Chem. Phys.1960, 32, 1505.
28. Laidler, K., Physical Chemistry. Houghton Mifflin College 1999
29. Letherby, H. J., Chem. Soc. vol.15, 1862, p.161.
30. 江文彥，科學發展，第359期，2002年11月，p68-71
31. 蕭如娟，”導電塑膠”，科儀新知， vol.9, Jun.1988, p.65
32. Kittel, C., Introduction to Solid State Physics. 6th ed., John Wiley &; Son, Singapore, 1986
33. Misra, P., Optical polarization anisotropy in nonpolar GaN thin films due to crystal symmetry and anisotropic strain,Humboldt-university,PhD thesis,2005
34. Yu, P. Y., Fundamentals of Semiconductors,Springer,2001.
35. Nardes AM. On the conductivity of PEDOT:PSS thin films. 2007.
36. Poly（3,4-ethylenedioxythiophene） and Its Derivatives: Past, Present, and Future
37. Louwet, F. et al., PEDOT/PSS: synthesis, characterization, properties and applications.Synthetic Metals 135-136, 115-117 ,2003.
38. Louwet, F,; Groenendaal, L.; Dhaen ,J.; Manca, J.; Van Luppen, J.; Verdonck, E. et al. PEDOT/PSS: synthesis, characterization, properties and applications. Synthetic Metals. 2003;135–136 0 :115-7.
39. Chun-Hsuan Lin K-TC,; Jeng-Rong Ho,; J.-W. John Cheng,; Raymond Chien-Chao Tsiang., PEDOT:PSS/Graphene Nanocomposite Hole-Injection Layer in Polymer Light-Emitting Diodes. Nanotechnology. 2012:7
40. de Kok, M. M.; Buechel1, M.; S. I. E. Vulto,; van de Weijer, P.; Meulenkamp, E. A.; de Winter, S. H. P. M.; Mank, A. J. G.; Vorstenbosch, H. J. M.; Weijtens, C. H. L.; van Elsbergen, V., Phys. Stat. Sol. （A） 2004, 201, 1342.
41. Baldo DFOB, M. A.; Shoustikov, Y.; You, A.; Sibley, S.; Thompson, M. E.; Forrest. S. R., Highly efficientphosphorescent emission from organic electroluminescent devices. Nature. 1998;395:151-4.
42. Cheng, Y. J.; Yang, S. H.; Hsu, C. S. Chem. Rev. 2009, 109, 5868.
43. (a) Halls, J. J. M.; Pichler, K.; Friend, R. H.; Moratti, S. C.; Holmes, A. B. Appl. Phys.Lett. 1996, 68, 3120. (b) Theander, M.; Yartsev, A.; Zigmantas, D.; Sundstrom, V.;Mammo, W.; Andersson, M. R.; Inganas, O. Phys. Rev. B 2000, 61, 12957. (c)
88Haugeneder, A.; Neges, M.; Kallinger, C.; Spirkl, W.; Lemmer, U.; Feldmann, J.; Scherf,U.; Harth, E.; Gu¨gel, A.; Mullen, K. Phys. Rev. B 1999, 59, 15346. (d) Stubinger, T.;Brutting, W. J. Appl. Phys. 2001, 90, 3632. (e) Markov, D. E.; Amsterdam, E.; Blom, P.W. M.; Sieval, A. B.; Hummelen, J. C. J. Phys. Chem. A 2005, 109, 5266.
44. 黃金鑫，“OLED 有機電激發光材料與元件”，五南出版社 （2005）。
45. Jenny Nelson., The Physics of Solar Cells., Imperial College Press, (2003)
11-14.
46. You, Z.Z,; Dong, J. Y., Oxygen plasma treatment effects of indium-tin oxide in organic light-emitting devices. Vacuum. 2007;81（7）:819-25.
47. van Dijken, A.; Perro, A.; Meulenkamp, E.A.; Brunner, K., The influence of a PEDOT:PSS layer on the efficiency of a polymer light-emitting diode. Organic Electronics. 2003;4（2–3）:131-41.
48. M,Y.Se, et al. Photovoltaic characteristics of TiO2/conjugated polymer junctions. Synthetic Metals. 2003:1387-8.