本研究以製備具有重複讀寫能力的偶氮苯複合材料，作為光學儲存上的應用。選用甲基紅2-{[4-(二甲氨基)苯基]偶氮基}苯甲酸(2-{[4-(dimethylamino)phenyl]diazenyl}benzoic acid, Methyl Red,簡稱MR)做為光致變色單體，分別與三種較低分子量的基材、以及一種高分子基材，利用離子鍵結形成複合材料。由於偶氮苯的順式-反式有不同的折射率，故可藉由全像技術製作相位光柵，又因為順式-反式結構具有可逆反應的特性，所以具備重複擦寫的功能。
使用不同基材的目的，在於嘗試製備反應速度快與繞射效率高的材料。三種較低分子量的基材分別為2-(3-氨基丙基)胺(Bis(3-aminopropyl)amine, 簡稱BAA)、聚丙烯胺-丙胺枝狀物(Polypropylenimine tetramine dendrimer, 簡稱PPI)、三羥甲丙烷三聚丙二醇醚(氨基封端)({Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether},簡稱TPGA)，至於高分子基材則為3-氨基丙基三乙氧基矽烷((3-Aminopropyl)triethoxysilane, APTES簡稱AP)。這四種基材皆是以氨基與甲基紅形成離子鍵，一方面可以減少相分離的情形，另一方面有較強的分子作用力，相對於以氫鍵構成的複合材料而言，具備較高的熱穩定性，有利於長時間保存。
材料合成與鑑定分析方面，透過核磁共振儀(NMR)、傅立葉轉換紅外線光譜(FTIR)確認鍵結的形成，再利用熱重分析儀(TGA)分析複合材料之熱穩定性質。在光學儲存元件的測試方面，量測各光學儲存元件的繞射效率、光柵形成速度、厚度起伏、與折射率變化。
由實驗結果得知，在材料鑑定部份，這四種基材皆與甲基紅形成離子鍵結，且熱穩定性隨基材分子量增加而提升。在光學元件的測試部份，MR/BBA、MR/PPI、MR/TPGA、MR/AP的最高繞射效率分別為17%、16%、18% 與19%。光柵形成速度隨著基材分子量的減少而增快，同時產生多階繞射的速度也隨著增快。另外，基材分子量越小，伴隨光柵產生的表面起伏就越大，而樹枝狀基材(dendrimer)的分枝越多，偶氮苯受光轉動排列時的立體障礙就越大，導致表面起伏變小。

In this study, we prepared several azobenzene composites for optical storage. The light-induced interconversion allows azobenzene composites to be used as rewritable and erasable optical storage materials. Four different materials were selected as the incorporating materials, which were used to combine with the azobenzene material (2-{[4-(dimethylamino)phenyl]diazenyl} benzoic acid, Methyl Red, MR). They were ((3-Aminopropyl)triethoxysilane, APTES, AP), (Bis(3-aminopropyl)amine, BAA), (Polypropylenimine tetramine dendrimer, PPI) and ({Trimethylolpropane tris[poly(propylene glycol), amine terminated] ether}, TPGA). These azobenzene composites were formed by ionic bonding, which reduces the oppertunity of the phase separation and enhances the thermal stability for long term preservation.
The diffraction efficiency of the composites MR/AP, MR/BAA, MR/PPI, MR/TPGA, were 19%, 17%, 16% and 18%. Atomic force microscopy revealed that surface variation of these composites was 768,758, 1467 and 729 nm, respectively, while N&K results show that the sample thickness before holographic recording was 1422nm、1047nm、2148nm、762nm, respectively.

論文審定書 i
誌謝 ii
摘要 iii
Abstract v
目錄 vi
圖目錄 ix
表目錄 xii
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 4
第二章 原理與文獻回顧 6
2.1 全像術 6
2.1.1 薄光柵與厚光柵 7
2.1.2繞射效率計算方式 9
2.2 偶氮苯化合物的光致變色反應 9
2.2.1 光致變色反應 9
2.2.2 偶氮苯化合物之順反異構型態 11
2.3 以偶氮苯材料作為全像術儲存材料 13
2.3.1表面起伏光柵(Surface relief grating)與折射率變化 13
2.3.1 各式偶氮苯複合材料作為全像術儲存之優劣與特性分析 14
第三章 研究方法 16
3.1 實驗藥品及材料 16
3.2 實驗流程 17
3.2.1 MR/AP製程 17
3.2.2 MR/BAA製程 18
3.2.3 MR/PPI製程 19
3.2.4 MR/TPGA製程 20
3.3 材料的實驗儀器及分析方法 21
3.3.1 傅立葉轉換紅外光譜儀 (Fourier transform infrared spectroscopy, FTIR) 21
3.3.2 核磁共振光譜儀(Nuclear Magnetic Resonance Spectroscopy, NMR) 22
3.3.3 旋轉塗佈機(Spin Coater) 22
3.4 全像干涉紀錄與讀取 23
3.4.1 波前紀錄與波前重建 23
3.5 光學性質檢測儀器 25
3.5.1 原子力顯微鏡(Atomic Force Microscope, AFM) 25
3.5.1 光學顯微鏡(Optical Microscope, OM) 26
3.5.2 薄膜特性分析儀(N&K) 26
第四章 結果與討論 27
4.1 . 材料的合成鑑定 27
4.1.1 NMR核磁共振光譜儀檢測(NMR) 27
4.1.2 傅利葉轉換紅外線光譜儀(FTIR) 38
4.1.3 TGA熱重分析儀(TGA) 46
4.2 光學特性 53
4.2.1 材料的繞射效率檢測 53
4.2.1 薄膜特性及∆n分析(N&K) 60
4.2.2 光學顯微鏡(OM)分析 61
4.2.3 掃描式電子顯微鏡(SEM) 63
4.2.4 原子力顯微鏡 65
第五章 結論 72
參考文獻 73

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