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研究生: 陳思聖
Chen, Sz-Sheng
論文名稱: 聚苯胺衍生物之合成分析與在發光二極體之應用
Polyaniline derivatives:synthesis, characterization and applications in light-emitting diodes
指導教授: 溫添進
Wen, Ten-Chin
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2003
畢業學年度: 91
語文別: 英文
論文頁數: 98
中文關鍵詞: 聚苯胺發光二極體
外文關鍵詞: polyaniline, light-emitting diodes
相關次數: 點閱:72下載:1
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  • 本研究主要是研究以電化學方法,在含有過氯酸鋰的碳酸丙烯溶液中,以不同的進料比聚合2,5-二甲氧苯胺與2,2-雙硫二苯胺共聚物,而後以循環伏安掃瞄、光電化學行為及傅利葉轉換紅外線光譜,來分析共聚物與聚2,5-二甲氧苯胺/聚2,2-雙硫二苯胺在光學特性與結構上的不同;共聚物與純聚物的組成的鑑定則是利用X射線光電子光譜所得到;由掃描式電子顯微鏡可觀察共聚物與純聚物之間表面型態的差異。
    本實驗室已廣泛地研究過許多不同種類的聚苯胺衍生物,而目前一個有趣又熱門的題目,便是聚苯胺在有機發光二極體中當作電洞注入層的應用,其中針對聚苯胺衍生物在這方面所做的研究,則是比較少的;我們選擇同時擁有聚對苯胺與苯胺性質的聚二苯胺,在此研究中,我們以紫外光-可見光光譜、傅利葉轉換紅外線光譜、熱重分析法與循環伏安掃瞄來特徵分析聚二苯胺摻雜樟腦磺酸的系統,此外,我們更進一步組裝有機發光二極體,利用聚二苯胺摻雜樟腦磺酸來當作電洞注入層,並且選擇MEH-PPV為發光層的有機發光二極體元件,來探討聚二苯胺摻雜樟腦磺酸對於元件性質的影響。

    In this research, copolymers of 2,5-dimethoxy aniline (DMA) with 2,2-dithiodianiline (DTDA) were prepared for different molar feed ratios of DTDA by electrochemical polymerization in propylene carbonate (PC) containing 1 M LiClO4. Cyclic voltammetry, UV-visible spectroelectrochemical measurements and FTIR spectroscopy were used to identify the differences in optical properties and structures between the copolymer and the homopolymers (PDMA/PDTDA). The composition of the copolymer was determined by X-ray photoelectron spectroscopy (XPS) for the copolymers prepared with different feed ratios of comonomers. The fraction of DTDA units in the copolymers depends on the molar feed composition of DTDA in copolymerization. Scanning electron microscopy (SEM) reveals the morphological differences between the copolymer and PDMA.
    Many PANI derivatives have been extensively studied in our laboratory. It is an interesting topic to understand what effects will present in the PLED device using PANI derivatives as the hole-injection electrode. Although various reports on PANI from this aspect are available in literature, little attention has been paid to substituted derivatives of PANI. Poly(diphenylamine) (PDPA) is expected to possess the properties of poly(paraphenylene) and PANI. Hence, PDPA shows many special properties in electrochemistry, conductivity and electrochromism. In this work, the characterization of PDPA doped with camphor sulfonic acid (CSA) system will be studied through the examination of UV-Vis spectral, FTIR spectral, TGA and energy level. In addition, the polymer light emitting diodes fabricated with PDPA-CSA as a hole-injection layer. To investigate the effects of the PDPA-CSA on the performance of this PLED device, the characteristics of polymer light emitting diodes based on a single layer (MEH-PPV) and double layer (PDPA-CSA/MEH-PPV) are also compared.

    Abstract…………………………………………………………………...........I 中文摘要………………………………………………………......................III Acknowledgement…………………………………...………………….……IV Contents……………………………………………………………………….V List of Schemes……………………………………………………………….VIII List of Tables………………………………………………………………VIII List of Figures……………………………………………………………….....X Symbols and abbreviations…………………………………………………….XII Chapter 1 Introduction…………………………………………………….1 1-1 Conducting polymer…………………………………………………………1 1-1-1 Evolution of conducting polymer…..……………………………………..1 1-1-2 Classification of conducting polymer……………………………………3 1-1-3 Synthesis of conducting polymer………………………………………….4 1-1-4 Electronic conduction mechanisms……………………………………….5 1-1-5 Applications……………………………………………………………….7 1-2 Polyaniline and polyaniline derivatives……………………………………..10 1-2-1 Chemical and electrochemical polymerization of polyaniline…………..10 1-2-2 Electrochemical and electrochromic properties………………………….12 1-2-3 Processability of polyaniline……………………………………………..12 1-2-4 Polyaniline derivatives…………………………………………………...13 1-2-4-1 Ring-substituted polyanilines………………………………………...14 1-2-4-2 N-substituted polyanilines……………………………………………15 1-2-4-3 Other soluble PANI derivatives………………………………………16 1-2-5 Copolymer of polyaniline derivatives…………………………………...16 1-3 Basic concepts of organic light-emitting diodes…………………………….17 1-3-1 Structure of organic light-emitting diodes……………………………….18 1-3-2 Principles of organic light-emitting diodes operation……………….…..19 1-3-3 Polyaniline derivatives serve as hole-transporting layer……………..….21 1-4 Research motivation………………………………………………...……….22 Chapter 2 Electrosynthesis and characterization of a conducting copolymer having S-S links…………………………………..35 2-1 Introduction………………………………………………………………….35 2-2 Experimental……………………………………………………………...…37 2-2-1 Reagents and instruments………………………………………………..37 2-2-2 Electropolymerizations of copolymer/homopolymers…………………..37 2-2-3 Spectrochemical studies on copolymer/homopolymers…………………38 2-2-4 FTIR Spectroscopy………………………………………………………39 2-2-5 Scanning electron microscopy…………………………………………...39 2-2-6 X-ray photoelectron spectroscopy……………………………………….39 2-3 Results and discussion………………………………………………………39 2-3-1 Cyclic voltammetry………………………………………………...……40 2-3-2 Spectroelectrochemistry…………………………………………………42 2-3-3 FTIR Spectroscopy………………………………………………………43 2-3-4 Scanning electron microscopy…………………………………….……..44 2-3-5 X-ray photoelectron spectroscopy……………………………………….44 2-3-6 Solubility…………………………………………………………………45 2-4 Conclusion………………..…………………………………………………45 Chapter 3 Poly(diphenylamine) doped with camphor sulfonic Acid:synthesis, characterization and applications in organic light-emitting diodes………………………………………….61 3-1 Introduction………………………………………………………………….61 3-2 Experimental………………………………………………………………...63 3-2-1 Chemicals………………………………………………………………..63 3-2-2 Preparation of poly(diphenylamine)……………………………………..63 3-2-3 Characterization of PDPA-CSA………………………………………….63 3-2-4 Fabrication and measurement of PLED devices…………………………64 3-3 Results and discussion………………………………………………………64 3-3-1 UV-Vis spectral……………………………………………………….…64 3-3-2 FTIR spectroscopy………………………………………………………66 3-3-3 Thermal gravimetric analysis……………………………………………66 3-3-4 Scanning electron microscopy (SEM)…………………………………..67 3-3-5 Atomic force microscopy (AFM)………………………………………..67 3-3-6 Energy level of PDPA……………………………………………………68 3-3-7 I-V characteristic and Brightness………………………………………..69 3-4 Conclusions………………………………………………………………….71 Chapter 4 Summary………………………………………………………86 References…………………………………………………………………………………87 Publication List…………………………………………………………………………..97 Conference Paper………………………………………………………………………...97 Bibliography……………………………………………………………………………....98

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