臺灣博碩士論文加值系統

近二十年來科學家致力於合成高共軛的導電高分子，不論是在光學活性上或是一些的電性質上，都有很濃厚的興趣。而我們希望以簡單且有效的方法合成一個三度空間結構的聚苯胺，提高其抗溶性而增加其應用性，尤其是在發光二極體元件上。
利用韓建中老師及實驗室的學長所發展的同步還原與取代反應，我們成功地以HSCH2CH2SH建立一個三度空間的高網狀交聯的聚苯胺。利用循環伏特安培法（cyclic voltammetry）、傅利葉轉換紅外線光譜儀（FT-IR）、紫外光光譜儀（UV-Vis-NIR）、X光光電子能譜儀（XPS）、二次離子質譜儀（SIMS）、四點探針導電儀等方法鑑定分析，更確信此乃有效且可控制交聯程度的方法。
藉由CV圖譜和UV-Vis的吸收光譜得到聚苯胺和各聚合物的HOMO、LUMO和能隙等相關電子能階，更有利於對材料間的選擇，且量測的聚苯胺HOMO為4.8 eV，適合作為ITO導電玻璃和發光材料間的電洞傳輸層。以旋轉塗佈法塗佈在ITO上的聚苯胺薄膜，透過表面分析可知其表面均勻平整。另一方面我們以電化學的氧化聚合方法在ITO上得到不錯的聚苯胺薄膜，以同步還原與取代反應，再建立一個三度空間的高網狀交聯的聚苯胺，以增強其抗溶性、附著力及薄膜的機械強度，而提高其應用性。

Researches on conjugated conducting polymers have been actively pursued in the last two decades due to the scientific and industrial interests on their unique optical and electronic properties. One of the recent interesting focuses is on the electroluminescence property of conjugated polymers. Polyanilines, with a relative low oxidation state and a rather light coloring in its conductive form, has been demonstrated to be a good hole-transport material in its neutral form and also as a good candidate material for transport positive electrode.
The major drawbacks of using polyanilione as a hole-transport layer is the relative poor adhesion of polyaniline to ITO glass electrode, which often resulted in the peeling off of the polyaniline coating and therefore led to the poor reliability and shorter life of the corresponding LED (Light Emitting Diode) devices.
To prepare a better adhered and more reliable polyaniline hole-transport layer we have devised a new reaction treatment to convert polyaniline matrix into a highly cross-linked matrix, which is based on our recently discovered concurrent reduction and substitution chemistry for polyanilines.
Heeger et al. demonstrated that when doped PAni or combination of doped PAni and ITO was used as the transparent anode for a polymer LED of MEH-PPV, the device performance can be significantly improved. Although a HOMO value of 4.8 eV had been assigned for the polyaniline materials, the detailed information about how the value was obtained was however lack of. Nor the origin of the HOMO data (whether associated with either doped PAni or undoped PAni) was specified. Furthermore, the LUMO and bandgap information were also not reported. Our preliminary results indicated that the HOMO, LUMO, and bandgap of the undoping emeraldine base form of PAni is 4.9, 3.4, and 1.5 eV

目錄
摘要 i
目錄 ii
圖目錄 v
表目錄 xi
第一章 緒論 1
第二章 文獻回顧 6
2-1 有激發光二極體的起源和發展 6
2-2 聚苯胺在LED元件上的應用 11
2-3 導電高分子聚苯胺的簡介 14
2-3-1 聚苯胺的歷史 14
2-3-2 聚苯胺的合成 14
2-3-3 聚苯胺的電化學 15
2-3-4 聚苯胺的紅外光光譜研究 17
2-4 三維網狀導電高分子的發展 20
第三章 實驗內容 22
3-1 藥品 22
3-2 電極製作與試劑配製 23
3-2-1 電極的製作 23
3-2-2 試劑的配製 23
3-3 製備聚苯胺與三維網狀聚苯胺（PAni-SCH2CH2S-PAni） 25
3-3-1製備聚苯胺 25
3-3-2 利用同步還原取代反應製備三維網狀聚苯胺 26
3-4 儀器部分 27
第四章 三維網狀聚苯胺薄膜的結構鑑定與分析
前言 34
4-1 全反射式紅外光光譜的結果分析與討論 35
4-1-1 利用電化學方法氧化聚苯胺以進行同步還原與取代反應 35
4-1-2 利用電化學方法氧化聚苯胺以進行重複的同步還原與取代反應 37
4-2 循環伏特安培法的結果分析與討論 39
4-2-1 利用電化學方法氧化聚苯胺以進行同步還原與取代反應 39
4-2-2 以不同氧化態的聚苯胺來製備具有不同交聯程度的網狀聚苯胺 40
4-2-3 利用電化學方法氧化聚苯胺以進行重複的同步還原與取代反應 42
4-3 電子吸收光譜（UV-Vis-NIR）的結果分析與討論 44
4-3-1 以不同氧化態的聚苯胺來製備具有不同交聯程度的網狀聚苯胺 44
4-3-2 利用in-situ UV-Vis觀測聚苯胺不同的氧化態 47
4-3-3 利用電化學方法氧化聚苯胺以進行重複的同步還原與取代反應 49
4-4 電子能譜（ESCA）的光譜鑑定與分析討論 52
4-4-1 利用電化學方法氧化聚苯胺以進行同步還原與取代反應 52
4-4-2 以不同氧化態的聚苯胺來製備具有不同交聯程度的網狀聚苯胺 53
4-4-3 利用電化學方法氧化聚苯胺以進行重複的同步還原與取代反應 54
4-5 二次離子質譜儀（SIMS）的光譜鑑定與分析討論 55
4-6 溶解度的測試 57
4-6-1 以不同氧化態的聚苯胺來製備具有不同交聯程度的網狀聚苯胺 57
4-6-2 製備三維網狀聚苯胺（PAni-SCH2CH2S-PAni）的粉末 58
第五章 聚苯胺薄膜的電子能階鑑定與表面結構分析
前言 60
5-1 高分子的電子能帶分析與鑑定 62
5-2 聚苯胺的電子能帶分析與鑑定 66
5-2-1不同酸性下對聚苯胺氧化還原電位的影響 66
5-2-2不同電解質系統對氧化還原半電位的影響 68
5-2-3 聚苯胺的電子能階結構分析 69
5-3 聚苯胺薄膜的表面結構分析 73
5-4 聚苯胺薄膜的厚度量測分析 76
第六章 結論 79
第七章 參考文獻 80

(1) (a) Patil, A. O.; Heeger, A. J.; Wudl, F. Chem. Rew. 1988, 88, 183. (b) MacDiarmid, A. G.; Yang, L. S.; Huang, W. S.; Humphrey, B. D. Synth. Met. 1987, 18, 393. (c) Gustafsson, G.; Cao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, N.; Heeger, A. J. Nature 1992, 357, 477.
(2) Hyodo, K. Electrochim. Acta. 1994, 39, 265.
(3) MacDiarmid, A. G.; Yang, L. S.; Huang, W. S.; Humphrey, B. D. Synth. Met. 1987, 18, 393.
(4) Hoa, D. T.; Kumar, T. N. S.; Punekar, N. S.; Srinivasa, R. S.; Lai, R.; Contractor, A. Q. Anal. Chem. 1992, 64, 2645.
(5) Paul, E. W.; Ricco, A. J.; Wrighton, M. S. J. Phy. Chem. 1985, 89, 1441.
(6) Chao, S.; Wrighton, M. S. J. Am. Chem. Soc. 1987, 109, 6627.
(7) Osaheni, J. A.; Jenekhe, S. A.; Vanherzeel, H.; Meth, J. S. Chem. Mater. 1991, 3, 218.
(8) (a) One-Dimensional Metals: Physics and Materials Science; Roth, S. VCH: Weinheim, 1995. (b) Nishino, A. J. Power Sources 1996, 60, 137. (c) Yamamoto, H.; Oshima, M.; Fukuda, M.; Isa, I.; Yoshino, K. J. Power Sources 1996, 60, 173.
(9) Burroughes, J. H.; Bradley, D. D.C.; Brown, A. R.; Marks, R. N.; Mackay, K.; Friend, R. H.; Burns, P. L.; Holmes, A. B. Nature 1990, 347, 539.
(10) Gustafsson, G.; Gao, Y.; Treacy, G. M.; Klavetter, F.; Colaneri, N.; Heeger, A. J. Nature 1992, 357, 477.
(11) Pope, M.; Kallmann, H. P.; Magnante, P. J. Chem. Phys. 1963, 38, 2042.
(12) Kalinowski, J.; Godlewski, J.; Signerski, R. Mol. Cryst. Liq. Cryst. 1976, 33, 247.
(13) Tang, C.W.; VanSlyke, S. A. Appl. Phys. Lett. 1987, 51, 913.
(14) Ohmori, Y.; Uchida, M.; Muro, K.; Yoshino, K. Jpn. J. Appl. Phys. 1991, 30, L1941.
(15) Brown, A. R.; Bradley, D. C. C.; Burroughes, J. H.; Friend, R. H.; Greenham, N. C. Appl. Phys. Lett. 1992, 61, 2793.
(16) Greenham, N. C.; Moratti,S. C.; Bradley, D. C. C.; Friend, R. H.; Holmes, A. B. Nature 1993, 365, 628.
(17) Kido, J.; Hongawa, K.; Okuyama, K.; Nagai, K. Appl. Phys. Lett. 1993, 63, 2627.
(18) Braun, D.; Heeger, A. J. Appl. Phys. Lett. 1991, 58, 1982.
(19) Yang, Y.; Heeger, A. J. Appl. Phys. Lett. 1994, 64, 1245-1247.
(20) Heeger, A. J.; Parker, I. D.; Yang, Y. Synth. Met. 1994, 67, 23-29.
(21) Letheby, H. J. Chem. Soc. 1862, 15, 161.
(22) Green, A. G.; Woodhead, A. E. J. Chem. Soc. Trans. 1910, 97, 2388.
(23) Langer, J. Solid State Commun. 1978, 26, 839.
(24) Macdiarmid, A. G.; Chiang, J. C.; Halpern, M. ; Huang, W. S.; Mu, S. L.; Somasir, N. L. D.; Wu, W. ; Taniger, S. I. Mol. Cryst. Liq. Cryst. 1985, 121, 173.
(25) Macdiarmid, A. G.; Epstein, A. J. Faraday Discuss Chem. Soc. 1989, 88, 317.
(26) Focke, W. W.; Wenk, G. E.; Wei, Y. J. Phys. Chem. 1987, 91, 5813.
(27) Macdiarmid, A. G.; Chiang, J. C.; Richter, A. F.; Somasiri, N. L. D.; Epstein, A. J. “Polyaniline : Sythesis and Characterization of the Emeraline Oxidation State by Elemental Analysis” in L. Alca’cer(ed). “Conducting Polymer” D. Reidel Pub. Comp. Dordrecht, Holland 1987, 105.
(28) Travers,;J. P.; Chroboczek, J. ; Devreux, J.; Genoud, F. ; Nechtschein, M.; Syed, A.; Genies, E. M.; Tsintavis, C. Mol. Cryst. Liq. Cryst. 1985, 121, 195.
(29) Mohilner, D. M.; Adams, R. N.; Argersinger, W. J. J. Am. Chem. Soc. 1962, 84, 3618.
(30) Watanabe, A. K.; Mori, K.; Iwasaki, Y.; Nakamura, Y. Macromolecules 1987, 20, 1793.
(31) Huang, W. S.; Humphrey, B. D.; MacDiarmid, A. G., J. Chem. Soc. Farady. Trans., 1986, 82, 2385.
(32) Huang, W. S.; Humphrey, B. D.; MacDiarmid, A. G. J. Chem. Soc. Farady. Trans. 1. 1986, 82, 2385.
(33) Mercouri, G. K.. C&EN 1990, Dec. 3, 36.
(34) MacDiarmid, A.G.; Manhar, S. K.; Masters, J. G.; Sun, Y.; Weiss, H.; Synth. Met. 1991, 41-43, 621.
(35) Kobayashi, T.; Yoneyama, H.; Tamara, H. J. Electroanal. Chem. 1984, 177, 293.
(36) Kabumoto, A.; Shinozaki, K. Synth. Met. 1988, 26, 349.
(37) Neugebane, H.; Neckel, A. Synth. Met. 1989, 29, E185.
(38) Neugebane, H.; Neckel, A. Synth. Met. 1989, 29, E193.
(39) Han, C. C.; Jeng, R. C. Chem. Commun. 1997, 6, 553.
(40) Jang, J.; Jing, X.; Wang. B.; Wang, F. Synth. Met. 1988, 24, 231.
(41) Cao, Y. Synth. Met. 1990, 35, 319.
(42) Harada, I.; Furukawa, Y.; Veda, F. Synth. Met. 1989, 29, E303.
(43) Noel, P.; Genies, E. M.; Synth. Met. 1989, 29, 5.
(44) Rebourt, E.; Pepin-Dopat, B.; Dinh, E.; Synth. Met. 1995, 69, 291
(45) G. Liu,; Michael, S. Freund.; Macromolecules 1997, 30, 5660.
(46) Bredas, J. L.; Silbey, R.; Boudreaux, D. S.; Chance, R. R.; J. Am. Chem. Soc. 1983, 105, 6555
(47) Eckhardt, H.; Shacklette, L. W.; Jen, K. Y.; Elsenbaumer R. L. J. Chem. Phys. 1989, 91, 1303
(48) Pei, J.; Yu, W. L.; Huang, W.; Macromolecules 2000, 33, 2462
(49) Osaheni, J. A.; Jenekhe, S. A.; Chem. Master. 1995, 7, 672
(50) Janietz, S.; Bradley, D. D. C.; Grell, M.; Giebeler, C.; Inbasekaran, M.; Woo, E. P.; Appl. Phys. Lett. 1998, 73, 2453
(51) Yang, C. J.; Jenekhe, S. A.; Macromolecules 1995, 28, 1180