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研究生： 余大全
Da-Cyuan Yu
論文名稱： 新型態共軛延伸之非線性光學高分子—主鏈型之研究
Integrating π-Electron of Chromophore and Conjugated Polymer – Main Chain System Study
指導教授： 薛敬和
Ging-Ho Hsiue
口試委員:
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： 2006
畢業學年度： 94
語文別： 中文
論文頁數： 116
中文關鍵詞： 非線性光學 、共軛高分子 、賓主型 、主鏈型 、喃 、咔唑
外文關鍵詞： Nonlinear Optical, NLO, Conjugated polymer, guest-host, main-chain, pyran, carbazole
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    • 本研究合成出發色團9-Hexyl-3,6-bis-[2-(4-nitro-phenyl)-vinyl]-9- H-carbazole (CzPhNO2)及2-{2,6-Bis-[2-(4-diethylamino-phenyl)-vinyl]- pyran-4-ylidene}-malononitrile (DCDEt)，利用Poly(N-vinyl carbazole) (PVK)及共軛高分子Polycarbazole (PCZ)，製備四組賓主型非線性光學薄膜—S1-a (PVK+CzPhNO2)，S1-b (PVK+PCZ+CzPhNO2)，S2-a (PVK+DCDEt)，S2-b (PVK+PCZ+DCDEt)。四組賓主型薄膜中，經由UV 吸收光譜測得其λonset而計算出之能隙值發現，於PVK中加入少量PCZ可以降低整體材料電荷轉移的能隙，將S1系列能隙從2.42eV 降至 2.40 eV，S2系列的能隙從2.07eV降至2.06eV。而從材料之配向極化發現加入PCZ之組別(S1-b, S2-b)其二階諧波強度均有些微提昇，S1系列其二階諧波強度從16.7提升至19.8 pm/V，S2系列從30.4提升至33.3 pm/V。PCZ的塑劑效應使材料的動態及時間穩定性降低，而CzPhNO2之嵌合效應則提升材料的穩定性。
    在主鏈型材料的研究上，利用2-(2,6-Diphenethyl-pyran-4- ylidene)-malononitrile分別進行Yamamoto聚縮合及Suzuki 偶合成功合成出一系列具主鏈共軛結構之非線性光學高分子P1、P2、P3。三個高分子之Td/Tg分別為276℃/125.6℃(P1)、329.5℃/118.2℃(P2)及301.7℃/149.1℃(P3)。在配向極化過程中，P1展現最佳的二次非線性光學係數11.5pm/V，其次依序為P3及P2分別為9.1 pm/V及5.1 pm/V。材料之熱穩定性測試，在動態熱穩定性測試結果P1亦展現最佳的穩定性，P1、P2、P3之T0分別為100.4℃、86.4℃及81.3℃。

    Conjugated polymers used in NLO are investigated in this study. Poly(n-vinyl-carbazole) (PVK) and polycarbazole (PCZ) have been used as a host polymer. Two chromophores, 9-Hexyl-3,6-bis-[2-(4- nitro-phenyl)-vinyl]-9H-carbazole (CzPhNO2) and 2- {2,6- Bis- [2- (4- diethylamino-phenyl)-vinyl]-pyran-4-ylidene}-malononitrile (DCDEt), have been prepared and used in four guest/host NLO systems. The d33 value has been improved when PCZ was added. The anchoring effect of CzPhNO2 leads better thermal stability than DCDEt, meanwhile, the plasticizer effect of PCZ leads lower effective transition temperature (T0). UV-Vis spectra show apparent red-shift in each system after casting. Accordingly, π-aggregation may be one of the reasons which improve d33 of the material.
    Besides, three conjugated polymers have been synthesized successfully as main-chain NLO materials by self-polymerization and Suzuki coupling. The Td/Tg of the three polymers are 276℃/125.6℃(Poly(2-(2,6- distyryl-pyran-4-ylidene)-malononitrile)—P1), 329.5℃/118.2℃(Poly{2-[2-(2-Biphenyl-4-yl-vinyl)-6-styryl-pyran-4-ylidene]- malononitrile}—P2), and 301.7℃/149.1℃(Poly{(9,9-dihelxyl- 9H-fluorene-2,7-yldene)-alt—(2-{2,6-bis[2-(2-hexyloxyl-5-phenylene)vinyl]-pyran-4-ylidene}-malononitrile)} —P3). P1 performs the best SH intensity of 11.5 pm/V between the three polymers while p3 performs the best Tg. The temporal stability was investigated by tracing the SH coefficient as a function of temperature. The effective transition temperature of P1, P2, and P3 are 100.4℃, 86.4℃, and 81.3℃.

    第一章 非線性光學材料介紹 1 1.1 前言 1 1.2 非線性光學的起源 3 1.3 非線性光學原理及現象 4 1.3-1 非線性光學原理 4 1.3-2 非線性光學現象 9 1.4 非線性光學材料 16 1.4-1 無機材料 16 1.4-2 有機材料 17 1.5 非線性光學材料應用 25 第二章 文獻回顧 29 2.1 發色團結構與非線性光學特性之關聯 29 2.1.1 推拉電子基團之影響 29 2.1.2 共振結構之影響 30 2.2 二維結構非線性光學系統 39 2.3 主鏈共軛型之非線性光學系統 45 2.4 研究動機 47 第三章 實驗部分 49 3.1 試藥 49 3.2 物性檢測 51 3.3 全咔唑賓主型非線性光學系統 53 3.3-1 研究架構 53 3.3-2 材料合成步驟 54 3.3-3 高分子薄膜的製備 63 3.4 高分子薄膜製備與檢測裝置 64 3.4-1 發色團及高分子之熱性質分析 64 3.4-2 高分子薄膜的配向極化 64 3.4-3 二次非線性光學量測儀器裝置簡介 65 第四章 結果與討論 67 4.1 發色團及高分子之合成與結構鑑定 67 4.2 發色團及高分子之熱性質分析 76 4.2-1 熱重損失分析 76 4.2-2 熱微差掃瞄卡計分析 81 4.3 光學性質分析 84 4.3.1 賓主型材料之UV-Vis光學性質分析 84 4.3-2 主鏈型全共軛非線性光學高分子之UV-Vis光學性質分析 89 4.4 配向極化程序及非線性光學性質分析 92 4.4-1 最適極化條件測試 92 4.4-2 主鏈型全共軛非線性光學材料共平面性之探討 97 4.4-3 極化前後分子排列程度之探討 99 4.4-3 光學穩定性之研究 104 第五章 結論 111 參考文獻 113

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