以全共軛環狀高分子3-己烷基噻吩(poly-(3-hexylthiophene)，P3HT)及全共軛
雜環芳香族共聚高分子的聚[2,6-(4,4-双-(2-乙基烷基)-4H-五環[2,1-b;3,4-b′]雙噻
吩)-并-4,7(2,1,3-苯并噻二唑)](poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-
b;3,4-b′]dithiophene)-alt-4,7-(2,1,3-benzothiadiazole] ， PCPDTBT) 當作電子施體
(donor)，各自混摻有優良吸光性及導電性奈米碳球(carbon fullerence)之電子受體
(acceptor)：[6,6]-phenyl C61-butyric acid methyl ester (PC61BM)，作成單層太陽能
(photovoltaic) 電池， 其結構為ITO/PEDOT:PSS/polymer:PC61BM/LiF/Al 。在
P3HT:PC61BM 元件中探討主動層厚度、退火(annealing)時期與前置和後置退火
(pre- and post-annealing)之比較；PCPDTBT:PC61BM 元件中探討混摻濃度、主動
層厚度與加工溶劑所引發之光致電效應。
當P3HT:PC61BM 重量比為1:1 之元件經由前置和後置的退火後其最高光致
電轉換效率(ηp)為4.58 %，因為能有效增加主動層(active layer)與陰極間的接觸面
積；而PCPDTBT:PC61BM(1:2.5 重量比)元件最高ηp 為2.62 %。PCPDTBT:PC61BM
元件其ηp 不及P3HT:PC61BM 元件者，因為其高度相分離，未能形成完整的互穿
網路，阻礙電荷的傳輸，元件填充因子受限於38 %。不同PC61BM 摻雜濃度的
高分子溶液在相同塗佈轉速下有不同薄膜厚度，造成元件的ηp 大幅度地改變，當
固定元件主動層厚度其ηp 改變較小，顯示主動層厚度相對於PC61BM 濃度，影
響元件的光致電轉換效率(ηp)較大。從P3HT:PCPDTBT:PC61BM 的光吸收範圍可
知由原本可見(Vis)光區延伸至近紅外(NIR)光區，但隨著PCPDTBT 濃度的增加
對其ηp 並沒有幫助，因為P3HT 與PCPDTBT 兩者的載子移動率不平衡，阻礙電
荷載子的傳輸，所以其ηp 仍不及單一高分子摻雜衍生奈米碳球(PC61BM)者好。
高分子成膜溶劑的沸點大於高分子的玻璃轉換溫度(Tg)易產生元件的ηp 大於溶
成膜劑沸點較Tg 低者。

Fully conjugated coil-like polymer poly-(3-hexylthiophene) (P3HT) and aromatic
heterocyclic copolymer poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta-[2,1-b;3,4-b′]-
dithiophene)-alt-4,7-(2,1,3-benzothiadiazole] (PCPDTBT) were applied separately as
donors mixed with derivatized carbon fullerence [6,6]-phenyl C61-butyric acid methyl
ester (PC61BM) serving as an acceptor. Single layer photovoltaic cells of ITO/
PEDOT:PSS/polymer:PC61BM/LiF/Al were fabricated to study photovoltaic effect of
layer thickness, thermal annealing, composition variance, and processing solvent.
At a P3HT:PC61BM weight ratio of 1:1, the thermally annealed photovoltaic cells
achieved a conversion efficiency (ηp) of 4.58 % from enhanced contact between cathode
and active layer. At a PCPDTBT:PC61BM weight ratio of 1:1.25, the best ηp was 2.62
%. The efficiency difference was due to PCPDTBT:PC61BM was highly phase
separated preventing the formation of conductive interpenetrating network to facilitate
charge transport. Its device fill factor was limited to be 38 %. Under the same spin
coating speed, solutions of different PC61BM concentration would yield different spun
film thickness leading to large change in conversion efficiency (ηp). At a constant
active layer thickness, ηp tended to be stable indicating that ηp was affected more by
the layer thickness than by PC61BM concentration. A layer of mixing P3HT:
PCPDTBT: PC61BM would expand the absorption range from visible to near infrared.
However, an increased PCPDTBT concentration did not help ηp. This is due to charge
transport imbalance between P3HT and PCPDTBT leading to an ηp less than those of
individual blends with PC61BM. Device ηp was consistently higher for using a
solvent with a boiling point higher than polymer glass transition temperature (Tg).

圖目錄…………………………………………………………………………… .. .VIII
表目錄…………………………………………………………………………….. .XIV
第一章、 緒 論 ........................................................................................................... 1
1-1 前言 .................................................................................................................... 1
1-2 研究動機 ............................................................................................................ 2
第二章、 文獻回顧 ....................................................................................................... 4
2-1 材料介紹 ............................................................................................................ 4
2-1-1 陽極(Anode) [3] .................................................................................. 4
2-1-2 陰極(Cathode) [4] ............................................................................... 5
2-1-3 氟化鋰(Lithium Fluoride，LiF) ....................................................... 6
2-1-4 連接層(Intermediate Layer) .............................................................. 6
2-1-5 P3AT 共軛高分子 ............................................................................. 7
2-1-6 PCPDTBT 共軛共聚合高分子 ......................................................... 8
2-1-7 PEDOT:PSS 電洞傳導層 .................................................................. 9
2-1-8 PC61BM 電子傳輸材料 .................................................................. 10
2-2 元件結構 ........................................................................................................... 11
2-2-1 單層結構 ......................................................................................... 11
2-2-2 雙層異質界面結構 ......................................................................... 11
2-2-3 混合層異質界面結構 ..................................................................... 12
2-2-4 疊層式結構 ..................................................................................... 12
2-3 應用原理 .......................................................................................................... 13
2-3-1 能量與電荷轉移機制 ..................................................................... 13
2-3-2 太陽光模擬 ..................................................................................... 14
2-3-3 光電轉換原理 ................................................................................. 17
2-3-4 太陽能電池等效電路 ..................................................................... 19
2-3-5 光電特性參數 ................................................................................. 21
第三章、 實驗內容 ..................................................................................................... 23
3-1 實驗流程圖與光致電能階圖 .......................................................................... 23
3-2 實驗材料 .......................................................................................................... 25
3-3 實驗步驟 .......................................................................................................... 26
3-3-1 溶液配製 ......................................................................................... 26
3-3-2 元件製程. ........................................................................................ 27
3-4 製程設備 .......................................................................................................... 28
3-4-1 超音波清洗機(Ultrasonic Cleaner) ................................................ 28
3-4-2 磁式旋轉加熱盤(Hot Plate)............................................................ 29
3-4-3 氧電漿(O2 Plasma)清洗機 .............................................................. 29
3-4-4 旋轉塗佈機(Spin Coater)................................................................ 29
3-4-5 手套箱(Glove Box)系統 ................................................................. 30
3-4-6 真空熱蒸鍍機(Vacuum Thermal Evaporator) ................................ 31
3-5 量測儀器 .......................................................................................................... 32
3-5-1 太陽光模擬光源(Solar Simulator) ................................................. 32
3-5-2 掃描式電子顯微鏡(Scanning Electron Microscope，SEM) ......... 33
3-5-3 紫外光-可見光吸收光譜(UV-Vis Absorption Spectrum) .............. 34
3-5-4 微差掃描卡計(Differential Scanning Calorimeter，DSC)………36
第四章、結果與討論 .................................................................................................. 37
4-1 P3HT:PC61BM 單層有機太陽能電池 ........................................................... 37
4-1-1 薄膜厚度 ......................................................................................... 37
4-1-2 熱退火時段 ..................................................................................... 44
4-1-3 前置與後置退火之比較 ................................................................. 48
4-2 PCPDTBT:PC61BM 單層有機太陽能電池 ...................................................... 50
4-2-1 不同PC61BM 混摻濃度 ................................................................. 50
4-2-2 不同薄膜厚度 ................................................................................. 71
4-2-3 溶劑效應 ......................................................................................... 76
4-3 P3HT:PCPDTBT:PC61BM 單層有機太陽能電池 ........................................... 82
4-3-1 P3HT 與PCPDTBT 總濃度為0.5 wt. % ....................................... 82
4-3-2 P3HT 濃度為0.5 wt. % .................................................................. 87
第五章、總 結 ........................................................................................................ 100
第六章、參考文獻 .................................................................................................... 102

1. J. Y. Kim, K. Lee, N. E. Coates, D. Moses, T. -Q. Nguyen, M. Dante, and A. J. Heeger,
Science, 317, 222 (2007).
2. S. Sista, M.-H. Park, Z. Hong, Y. Wu, J. Hou, W. L. Kwan, G. Li, and Y. Yang, Adv.
Mater., 22, 380 (2010).
3. 紀國鐘，鄭晃忠，「液晶顯示器技術手冊」，台灣電子材料與元件協會，台北 (2004)。
4. V. D. Mihailetchi, P. W. M. Blom, J. C. Hummelen, and M. T. Rispens, J. Appl. Phys.,
94, 6849 (2003).
5. J. G. Xue, S. Uchida, B. P. Rand, and S. R. Forrest, Appl. Phys. Lett., 85, 5757 (2004).
6. A. Hadipour, B. de Boer, J. Wildeman, F. B. Kooistra, J. C. Hummelen, M. G. R.
Turbiez, M. M. Wienk, R. A. J. Janssen, and P. W. M. Blom, Adv. Funct. Mater., 16,
1897 (2006).
7. D. W. Zhao, X. W. Sun, C. Y. Jiang, A. K. Kyaw, G. Q. Lo, and D. L. Kwong, Appl.
Phys. Lett., 93, 083305 (2008).
8. A. G. F. Janssen, T. Riedl, S. Hamwi, H. H. Johannes, and W. Kowalsky, Appl. Phys.
Lett., 91, 073519 (2007).
9. W. Ma, C. Yang, X. Gong, K. Lee, and A. J. Heeger, Adv. Funct. Mater., 15, 1617
(2005).
10. D. Mühlbacher, M. Scharber, M. Morana, Z. Zhu, D. Waller, R. Gaudiana, and C. Brabec, Adv. Mater.,18, 2884 (2006).
11. Z. Zhu, D. Waller, R. Gaudiana, M. Morana, D. Mühlbacher, M. Scharber, and C.
Brabec, Macromolecules, 40, 1981 (2007).
12. J. Peet, N. S. Cho, S. K. Lee, and G. C. Bazan, Macromolecules, 41, 8655 (2008).
13. J. Peet, J. Y. Kim, N. E. Coates, W. L. Ma, D. Moses, A. J. Heeger, and G. C. Bazan,
Nat. Mat., 6, 497 (2007).
14. M. Pope, H. P. Kallmann, and P. Magnante, J. Chem. Phys., 38, 2042 (1963).
15. K. Petritsch, “Organic Solar Cell Architectures,” Ph.D. Thesis , Technisch-
Naturwissenschaftliche Fakult at der Technischen Universit, Graz (Austria) (2000).
16. 張正華，「有機與塑膠太陽能電池」，五南圖書出版公司，台北 (2007)。
17. P. W. Atkins, “Kurzlehrbuch Physikalische Chemie,” Wiley-VCH Verlag GmbH & Co.
KGaA, Germany (2001).
18. J. Xue, S. Uchida, B. P. Rand, and S. R. Forrest, Appl. Phys. Lett., 84, 3013 (2004).
19. C. J. Brabec, A. Cravino, D. Meissner, N. S. Sariciftci, T. Fromherz, M.T. Rispens, L.
Sanchez, and J. C. Hummelen, Adv. Funct. Mater., 11, 374 (2001).
20. C. Brabec, V. Dyakonov, J. Parisi, and N. S. Sariciftci, “Organic Photovoltaics,”
Springer, Berlin (2003).
21. C. Soci, I. W. Hwang, D. Moses, Z. Zhu, D. Waller, R. Gaudiana, C. J. Brabec, and A. J.
Heeger, Adv. Funct. Mater., 17, 632 (2007).
22. C. C. Wu, “Luminescence of Light Emitting Diodes of Fully Conjugated Heterocyclic
Aromatic Rigid-rod Polymer,” Ph.D. Thesis, National Sun Yat-Sen University
(Kaohsiung) (2003).
23. H. Y. Cheng, “Electrode Modifications of Molecular Light Emitting Diodes,” Master
Thesis, National Sun Yat-Sen University (Kaohsiung) (2003).
24. 施敏，「半導體元件物理與製作技術」，國立交通大學出版社，新竹 (2003)。
25. 陳金鑫，黃孝文，「有機電激發光材料與元件」，五南圖書出版公司，台北 (2006)。
26. H. C. Liao, “Package of Homojunction of Fully Conjugated Heterocyclic Aromatic
Rigid-rod Polymer Light Emitting Diodes,” Master Thesis, National Sun Yat-Sen
Univrsity (Kaohsiung) (2004).
27. F. Padinger, R. S. Rittberger, and N. S. Sariciftci, Adv. Funct. Mater., 13, 85 (2003).
28. Y. C. Huang, Y. C. Liao, S. S. Li, M. C. Wu, C. W. Chen, and W. F. Su, Solar Energy
Materials & Solar Cells, 93, 888 (2009)
29. P. M. Allemand, A. Koch, F. Wudl, Y. Rubin, F. Diederich, M. M. Alvarez, S. J. Anz,
and R. L. Wetten, J. Am. Chem. Soc., 113, 1050 (1991).
30. Y. Kim, S. A. Choulis, J. Nelson, D. D. C. Bradley, S. Cook, J. R. Durrant, Appl. Phys.
Lett., 86, 063502 (2005).
31. X. Yang, J. Loos, S. C. Veenstra, W. J. H. Verhees, M. M. Wienk, J. M. Kroon, M. A. J.
Michels, and R. A. J. Janssen, Nano Lett., 5, 579 (2005).
32. X. Yang, J. K. J. van Duren, R. A. J. Janssen, M. A. J. Michels, and J. Loos,
Macromolecules, 37, 2151 (2004).
33. T. Erb, U. Zhokhavets, G. Gobsch, S. Raleva, B. Stühn, P. Schilinsky, C. Waldauf, and
C. Brabec, Adv. Func. Mater., 15, 1193 (2005).
34. U. Zhokhavet, T. Erb, G. Gobsch, M. Al-Ibrahim, and O. Ambacher, Chem.Phys. Lett.,
418, 347 (2006).
35. H. Kim, W. W. So, and S. J. Moon, Solar Energy Materials & Solar Cells, 91, 581
(2007).
36. N. S. Sariciftci, L. Smilowitz, A. J. Heeger, and F. Wudl, Science, 258, 1474 (1992).
37. L. B. Wang, “Organic Photovoltaic Cells of Fully Conjugated Coil-like
Poly-(3-hexylthiophene) and Rod-like Heterocyclic Aromatic Polymer Doped with
Nano-carbon Particles,” Master Thesis, National Sun Yat-Sen University (Kaohsiung)
(2009).
38. G. Li, V. Shrotriya, J. Huang, Y. Yao, T. Moriarty, K. Emery, and Y. Yang, Nat. Mater., 4,
864 (2005).
39. V. Shrotriya, Y. Yao, G. Li, and Y. Yang, Appl. Phys. Lett., 89, 063505 (2006).
40. G. Dennler, M. C. Scharber, and C. J. Brabec, Adv. Mater., 21, 1323 (2009).
41. J. K. Lee, W. L. Ma, C. J. Brabec, J. Yuen, J. S. Moon, J. Y. Kim, K. Lee, G. C. Bazan,
and A. J. Heeger, Am. Chem. Soc., 130, 3619 (2008).
42. M. Caironi, T. Agostinelli, D. Natali, M. Sampietro, R. Cugola, M. Catellani, and S.
Luzzati, J. Appl. Phys., 102, 024503 (2007).
43. T. J. Savenije, J. E. Kroeze, X. Yang, and J. Loos, Thin Solid Films, 511-512, 2 (2006).