本研究利用溶膠-凝膠法，製備具有重複讀寫且快速寫入的偶氮苯全像材料，
可用於光學儲存、光學顯示等應用。溶膠-凝膠基材因為穩定性高且機械性質佳，
而有機基材受光照射後光柵會收縮，使其穩定性較差，所以本研究利用(4-
Aminoazobenzene, AAB)為偶氮苯感光單體，再選用 3-縮水甘油醚氧基丙基三甲氧
基矽烷((3-Glycidyloxypropyl)trimethoxysilane, GPTMS)為溶膠-凝膠基材與偶氮苯
進行開環反應形成共價鍵鍵結，藉由雷射光的同調性使偶氮苯分子進行可逆的順-
反式光異構化反應，製備出具有重複寫入能力的偶氮苯全像材料。
首先 AAB 與 GPTMS 製備偶氮苯全像材料，利用溶膠-凝膠法反應下的時間與
環境溫度為參數，探討偶氮苯全像材料在不同交聯程度下與開環程度所造成的繞
射效率之影響。
透過傅立葉轉換紅外光譜(FTIR)與核磁共振儀(NMR)可確認 AAB 與 GPTMS
形成共價鍵鍵結，再利用 FTIR 做定量分析可確認材料的鍵結率，藉由參數的變化
來調整鍵結率，製備出反應快速的偶氮苯全像材料。在固定反應溫度 60°C 下反應
8 小時，在 34 分鐘有最大繞射效率 34.11%；固定反應時間 4 小時加熱 80°C，在
31 分鐘有最大繞射效率 30.16%。藉由參數的趨勢來找出偶氮苯全像材料之最佳參
數，在反應溫度 65°C 下反應 8 小時，15 分鐘內達到 30.87%最大繞射效率；將樣
品濃度提高兩倍，反應溫度 80°C 下反應 8 小時，在 18 分鐘內達到最大繞射效率
30.01%。

Azobenzene molecules exhibit numerous photoresponsive features and the irradia-
tion of azobenzenes with polarized light results in a fast and efficient photoselective isom-
erization,accompanied by a chromophore motion and alignment.An azo chromophore (4-
Aminoazobenzene, AAB) was selected as the photosensitive monomer.The functional
epoxy used was ((3-Glycidyloxypropyl)trimethoxysilane, GPTMS).We have used ring
opening reaction of GPTMS,AAB was employed instead of the component providing for
the ring opening,whereas AAB become covalently bonded to GPTMS.
In this study, We found that the reaction time of the Sol-Gel process played an key
role to influence cross-linking degree of the GPTMS. Meanwhile, the reaction tempera-
ture might change the degree of bonding between AAB and GPTMS (AG).The main goal
is to achieve the efficient formation of (surface relief gratings, SRGs) and efficient Dif-
fraction Efficiency.
We found the optimal parameters to produce azobenzene holographic materials with
efficient formation of SRGs and efficient Diffraction Efficiency.The Diffraction Effi-
ciency of the composites AG was 30.87% and it could be achieved in 15 minutes. From
the data measurement by Atom Force microscopy (AFM), it revealed the SRGs depth of
AG were 40.8 nm.

論文審定書 I
誌謝 II
摘要 III
Abstract IV
目錄 V
圖目錄 VIII
表目錄 XII
第一章 緒論 1
1.1 前言1
1.2 全像術 2
1.3 光柵 3
1.3.1 體積光柵 4
1.3.2 薄光柵 5
1.4 繞射效率 5
1.5 全像儲存技術 6
1.6 全像儲存材料種類 7
1.6.1 鹵化銀材料(Silver halide emulsion) 7
1.6.2 重鉻酸鹽明膠(Dichromated Gelatin, DCG) 7
1.6.3 光折變材料(Photorefractive Crystal) 7
1.6.4 感光類材料(Photographic material) 8
第二章 原理與文獻回顧 10
2.1 偶氮苯全像材料文獻回顧 10
2.2 偶氮苯化合物的光學性質 14
2.2.1 光致變色反應 14
2.2.2 順反異構型態 15
2.2.3 表面起伏光柵(Surface Relief rating) 16
2.3 環氧乙烷 17
2.3.1 環氧乙烷之硬化反應 17
2.4 溶膠－凝膠法(Sol-Gel) 19
2.4.1 反應機制 19
2.4.2 控制變因 20
第三章 研究方法 23
3.1 研究動機與目的 23
3.2 實驗藥品及材料 25
3.2.1 樣品代號 26
3.3 實驗流程 26
3.3.1 材料 AG-nh 製程 26
3.3.2 材料 AG-m°C 製程 28
3.4 實驗儀器及分析方法 30
3.4.1 傅立葉轉換紅外光光譜儀(Fourier Transform Infrared Spectrometer,
FTIR) 30
3.4.2 核磁共振光譜儀(Nuclear Magnetic Resonance Spectroscopy, NMR) 30
3.4.3 光功率計(Power Meter) 30
3.4.3 旋轉塗佈機(Spin Coater) 31
3.4.4 三維輪廓儀(Alpha-step Profilometer) 31
3.4.5 原子力顯微鏡(Atomic Force Microscopy, AFM) 31
3.5 全像干涉實驗 31
3.5.1 實驗設備 31
3.5.2 全像記錄與讀取 32
第四章 結果與討論 34
4.1 材料的合成鑑定分析 34
4.1.1 核磁共振光譜儀分析(NMR) 34
4.1.2 傅立葉轉換紅外光光譜儀(FTIR) 37
4.1.3 三維輪廓儀分析(Alpha-step) 44
4.2 光學特性 49
4.2.1 Sol-Gel 基材 AG 之繞射效率 49
4.2.2 原子力顯微鏡分析(AFM) 59
4.2.3 光學特性綜合討論 68
4.3 全像材料 AG 之最佳參數 70
4.3.1 材料 AG-8h-65°C 70
4.3.2 材料 AG-9h-65°C 73
4.3.3 材料 AG-8h-80°C 76
4.4 厚度效應 79
4.5 實驗室團隊歷年研究綜合比較 84
第五章 結論 85
第六章 建議未來工作 86
參考文獻 87

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