針對以聚(三-己基噻吩)(P3HT)與富勒烯衍生物(PCBM)製成混摻異質界面太陽能電池，因於熱處理時兩材料相容性不佳，容易產生相分離導致分子各自有過度聚集之現象，造成薄膜形態不易控制之議題進行研究。
　　本研究將基於高分子結晶之特性，以恆溫結晶的方式製備具有高結晶性之P3HT，並於P3HT與PCBM之中加入末端醇基化之聚(三-己基噻吩)(HOC-P3HT-COH)，利用氫鍵作用力改善材料間相容性與薄膜上之分布，探討加入HOC-P3HT-COH之後對結晶形態之影響。
　　實驗將以熱差式掃描分析卡計(DSC)與X-ray繞射儀(XRD)研究其結晶特性上之差異，使用飛行時間(TOF)測量載子移動度，並以掃描式電子顯微鏡(SEM)觀察薄膜表面形態之變化，以及利用穿透式電子顯微鏡(TEM)探討薄膜中分子之分布形態；經由以上測量結果可得知添加HOC-P3HT-COH於145℃下恆溫結晶處理之薄膜中，P3HT可具有較佳之結晶與載子移動度並且PCBM將與P3HT有較好的相容性減少過度聚集之現象產生，有助於控制有機高分子太陽能電池之形態。

Bulk-heterojunction process has been widely used in organic solar cells. The active layer was thermally treated to enhance the morphology of active layer. Unfortunately, the thermal treatment process also induced phase separation between the p-type semiconductor and n-type semiconductor.
An isothermal crystallization process was applied to the fabrication of Poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butryic acid methyl ester (PCBM) based solar cells accompanied with a hydroxyl group end-functionalized poly(3-hexylthiophene) (HOC-P3HT-COH). HOC-P3HT-COH compatibilized the P3HT and PCBM active layer and also homogenized the distribution of P3HT/PCBM active layer. The isothermal crystallization process was then applied to the active layer to study the crystallization behavior of the active layer comparing to the conventional spin-coating process.
Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) were used to characterize the crystallization behavior. Scanning electron microscope (SEM) was used to probe the surface morphology of the active layer. Transmission electron microscope (TEM) was used to investigate the morphology of P3HT/PCBM layer.
Experimental results indicated that P3HT/PCBM layer achieved a better crystal form than the thermal treatment process and the carrier mobility was enhanced by ten times which is favorable for the solar cells applications.

Abstract I
摘要 II
目錄 III
圖目錄 VI
表目錄 XII
第一章 緒論 1
1-1 前言 1
1-2 有機高分子太陽能電池簡介 2
1-2-1 有機高分子太陽能電池基本結構 2
1-2-2 有機高分子太陽能電池結構演進 4
1-2-2 有機高分子太陽能電池發電原理 6
第二章 研究背景與目的 10
2-1 研究背景 10
2-1-1 溶劑性質的選擇 11
2-1-2 電子施體與電子受體的組成比例 13
2-1-3 溶液濃度 15
2-1-4 材料的規則度 15
2-1-5 添加劑與互容劑 17
2-1-6 後處理條件 25
2-1-7 P3HT結晶特性之探討 29
2-2 研究動機與目的 33
第三章 實驗部分 38
3-1 實驗藥品與溶劑 38
3-2 實驗儀器 39
3-3 材料合成 41
3-3-1 OHC-P3HT-CHO之合成 41
3-3-2 HOC-P3HT-COH之合成 42
3-4 實驗步驟與流程 43
3-5 溶液配置 44
3-6 熱差式掃描分析卡計(DSC)實驗流程 45
3-7 測量載子移動度之樣品製備 46
3-8 固態薄膜製備 47
第四章 結果與討論 48
4-1 熱重力分析儀(TGA) 48
4-2 熱差式掃描分析卡計(DSC) 49
4-3 X-ray繞射儀(XRD) 59
4-4 載子移動度之飛行時間測量(TOF) 62
4-5 掃描式電子顯微鏡(SEM) 65
4-6 飛行時間二次離子質譜儀(TOF-SIMS) 69
4-7 穿透式電子顯微鏡(TEM) 72
第五章 結論 74
第六章 參考文獻 76
附錄一 81
附錄二 82
附錄三 83
附錄四 84

(1)Vak, D. J.; Kim, S.S.; Jo, J.; Oh, S.H.; Na, S.I.; Kim, J.W.; Kim, D.Y. Appl. Phys. Lett. 2007, 91, 081102.
(2)Michaelson H. B. J. Appl. Phys. 1977, 48, 4729.
(3)Chen, W. H.; Pan J. H.; Chou, Y. M. Chin. Chem. Soc. 2009, 67, 61.
(4)Huang, Y. J.; Chen, C. T. J. Chin. Chem. Soc. 2009, 67, 341.
(5)Kallmann, H.; Pope, M . J. Chem. Phys. 1959, 30, 585.
(6)Tang, C. W. Appl. Phys. Lett. 1986, 48, 183.
(7)Yu, G.; Pakbaz, K.; Heeger, A. J. Appl. Phys. Lett. 1994, 64, 3422.
(8)Yu, G.; Gao, J.; Hummelen, J. C.; Wudl, F.; Heeger, A. J. Sciene 1995, 270, 1789.
(9)Ma, W. L.; Yang, C. Y.; Gong, X.; Lee, K.; Heeger, A. J. Adv. Funct. Mater. 2005, 15, 1617.
(10)Chamberlain, G. A. Solar Cells 1983, 8, 47.
(11)Halls, J. J. M.; Pichler, K.; Friend, R. H.; Moratti, S. C.; Holmes, A. B. Appl. Phys. Lett. 1996, 68, 3120.
(12)Nunzi, J. M. C. R. Physique 3 2002, 3, 523.
(13)唐偉程, 應用奈米線與導電高分子製備複合太陽能電池, 國立成功大學航空太空工程研究所碩士論文, 2007。
(14)Yang, X. N.; Loos, J.; Veenstra, S. C.; Verhees, W. J. H.; Wienk, M.; Kroon, M.; Michels, M. H. J.; Janssen, R. A. J. Nano. Lett., 2005, 5, 579.
(15)Bao, Z.; Dodabalapur, A.; Lovinger, A. J. Appl. Phys. Lett. 1996, 69, 4108.
(16)Sirringhaus, H.; Tessler, N.; Friend, R. H. Science 1998, 280, 1741.
(17)Kobashi, M.; Takeuchi, H. Macromolecules 1998, 31, 7273.
(18)Sirringhaus, H.; Brown, P. J.; Friend, R. H.; Nielsen, M. M.; Bechgaard, K.; Langeveld-Voss, B. M. W.; Spiering, A. J. H.; Janssen, R. A. J.; Meijer, E. W.; Herweg, P.; Leeuw, D. M. de Nature 1999, 401, 685.
(19)Ali, K.; Pietsch, U.; Grigorian, S. J. Appl. Cryst. 2013, 46, 908
(20)Pandey, S. S.; Nagamatsu, S.; Takashima, W.; Kaneto, K. Jpn. J. Appl. Phys. 2000, 39, 6309.
(21)Pandey, S. S.; Takashima, W.; Nagamatsu, S.; Endo, T.; Rikukawa, M.; Kaneto, K. Jpn. J. Appl. Phys. 2000, 39, L94.
(22)Mozer, A. J.; Sariciftci, N. S. Chem. Phys. Lett. 2004, 389, 438.
(23)Yang, H. X.; Glynos, E.; Huang, B. Y.; Green, P. F. J. Phys. Chem. C 2013, 117, 9590
(24)Peumans, P.; Forrest, S. R. Appl. Phys. Lett. 2001, 79, 126.
(25)Chirvase, D.; Chiguvare, Z.; Knipper, M.; Parisi, J.; Dyakonov, V.; Hummelen, J. C. J. Appl. Phys. 2003, 93, 3376.
(26)Hoppe, H.; Sariciftci, N. S. J. Mater. Res. 2004, 19, 1924.
(27)Sariciftci, N. S.; Braun, D.; Zhang, C.; Srdanov, V. I.; Heeger, A. J. Appl. Phys. Lett. 1993, 62, 585.
(28)Shaheen, S. E.; Brabec, C. J.; Sariciftci, N. S.; Padinger, F.; Fromherz, T.; Hummelen, J. C. Appl. Phys. Lett. 2001, 78, 841.
(29)Hoppe, H.; Niggemann, M.; Winder, C.; Kraut, J.; Hiesgen, R.; Hinsch, A.; Meissner, D.; Sariciftci, N. S. Adv. Funct. Mater. 2004, 14, 1005.
(30)Martens, T.; D'Haen, J.; Munters, T.; Beelen, Z.; Goris, L.; Manca, J.; D'Olieslaeger, M.; Vanderzande, D.; De Schepper, L.; Andriessen, R. Synth. Met. 2003, 138, 243.
(31)van Duren, J. K. J.; Yang, X. N.; Loos, J.; Bulle-Lieuwma, C. W. T.; Sieval, A. B.; Hummelen, J. C.; Janssen, R. A. J. Adv. Funct. Mater. 2004, 14, 425.
(32)Hoppe, H.; Glatzel, T.; Niggemann, M.; Hinsch, A.; Lux-Steiner, M. C.; Saricftci, N. S. Nano Lett. 2005, 5, 269.
(33)Kim, Y.; Cook, S.; Tuladhar, S. M.; Choulis, S. A.; Nelson, J.; Durrant, J. R.; Bradley, D. D. C.; Giles, M.; Mcculloch, I.; Ha, C. S.; Ree, M. Nat. Mater. 2006, 5, 197.
(34)Urien, M.; Bailly, L.; Vignau, L.; Cloutet, E.; de Cuendias, A.; Wantz, G.; Cramail, H.; Hirsch, L.; Parneix, J. P. Polym. Int. 2008, 57, 764.
(35)Liu, J. G.; Han, Y. C. Polym. Bull. 2012, 68, 2145.
(36)Dang, M. T.; Hirsch, L.; Wantz, G.; Wuest, J. D. Chem. Rev. 2013, 113, 3734.
(37)Chang, Y. M.; Wang, L. Y. J. Phys. Chem. C 2008, 112, 17716.
(38)Chen, H. Y.; Yang, H. C.; Yang. G. W.; Sista, S.; Zadoyan, R.; Li, G.; Yang, Y. J. Phys. Chem. C 2009, 113, 7946.
(39)Sharma, S. S.; Sharma, G. D.; Mikroyannidis J. A. Sol. Energy Mater. Sol. Cells 2011, 95, 1219.
(40)Sivula, K.; Ball, Z. T.; Watanabe, N.; Frechet, J. M. J. Adv. Mater. 2006, 18, 206.
(41)Chan, S. H.; Lai, C. S.; Chen, H. L.; Ting, C.; Chen, C. P. Macromolecules 2011, 44, 8886.
(42)Kim, J. B.; Allen, K.; Oh, S. J.; Lee, S.; Toney, M. F.; Kim, Y. S.; Kagan, C. R.; Nuckolls, C.; Loo, Y. L. Chem. Mater. 2010, 22, 5762.
(43)Chen, Y. H.; Huang, P. T.; Lin, K. C.; Huang, Y. J.; Chen, C. T. Org. Electron. 2012, 13, 283.
(44)Padinger, F.; Rittberger, R. S.; Sariciftci, N. S. Adv. Funct. Mater. 2003, 13, 85.
(45)Erb, T.; Zhokhavets, U.; Gobsch, G.; Raleva, S.; Stuhn, B.;Schilinsky, P.; Waldauf, C.; Brabec, C. J. Adv. Funct. Mater. 2005, 15, 1193.
(46)Savenije, T. J.; Kroeze, J.; Yang, X.; Loos, J. Adv. Funct. Mater. 2005, 15,1260.
(47)Yang, X.; Loos, J.; Veenstra, S. C.; Verhees, W. J. H.; Wienk, M.; Kroon, M.; Michels, M. H. J.; Janssen, R. A. J. Nano. Lett. 2005, 5, 579.
(48)Tsoi, W. C.; Spencer, S. J.; Yang, L.; Ballantyne, A. M.; Nicholson, P. G.; Turnbull, A.; Shard, A. G.; Murphy, C. E.; Bradley, D. D. C.; Nelson, J.; Kim, J. S. Macromolecules 2011, 44, 2944.
(49)Joshi, S.; Grigorian, S.; Pietsch, U. Phys. Stat. Sol. 2008, 205, 488.
(50)Aryal, M.; Trivedi, K.; Hu, W. Nano Lett. 2009, 3, 3085.
(51)Brinkmann, M. J. Polym. Sci., Part B: Polym. Phys. 2011, 49, 1218.
(52)Yang, H. C.; Shin, T. J.; Yang, L.; Cho, K.; Ryu, C. Y.; Bao, Z. N. Adv. Funct. Mater. 2005, 15, 671.
(53)Vanlaeke, P.; Swinnen, A.; Haeldermans, I.; Vanhoyland, G.; Aernouts, T.; Cheyns, D.; Deibel, C.; D'Haen, J.; Heremans, P.; Poortmans, J.; Manca, J. V. Sol. Energy Mater. Sol. Cells 2006, 90, 2150.
(54)Huang, P. T.; Huang, P. F.; Horng, Y. J.; Yang, C. P. J. Chin. Chem. Soc. 2013, 60, 467.
(55)Avrami, M. J. Chem. Phys. 1939, 7, 1103.
(56)Avrami, M. J. Chem. Phys. 1940, 8, 212.
(57)Avrami, M. J. Chem. Phys. 1941, 9, 177.
(58)Yamamoto, S.; Kitazawa, D.; Tsukamoto, J.; Shibamori, T.; Seki, H.; Nakagawa, Y. Thin Solid Films 2010, 518, 2115.