本研究利用溶膠-凝膠法，製備應用在光學儲存的有機無機複合材料。以甲基丙烯酸丙酯三甲氧基矽烷(MAPTMS)作為前驅物，以TEOS作為基材，形成二氧化矽(SiO2)的網狀結構，並在網狀結構的孔洞內部填入單體、光起始劑(photoinitiator)、高折射率金屬前驅物(HRIS)，再藉由矽烷偶合劑(coupling agent)連接有機與無機相，形成有機-無機複合材料。以改變添加高折射率金屬前驅物的比例測量其對繞射效率的影響，當高折射率金屬前驅物添加量達到TM2時擁有最高繞射效率84.51±6.12%，相較於沒有添加高折射率金屬前驅物整整提升了40.41±3.21%。此材料也沒有明顯高階繞射現象，最大繞射效率為+1階。以N&K分析折射率差異(Δn)最大可達3.59*10-2，大於以Kogelnik’s coupled wave theory理論計算所得到的折射率差異。測量角度選擇性觀察進行多次寫入光柵所需的最小角度偏移量為2˚。Ramn分析發現TM5有Si-O-Zr鍵結生成，以AFM觀察形貌發現表面起伏微弱，材料單純是依靠折射率差異來形成光柵。實驗中使用綠光532nm的雷射光源記錄干涉條紋在全像光儲存材料上，利用調整全像光儲存材料的厚度和折射率，使滿足布拉格條件(Bragg condition)的繞射選擇性。

The organic-inorganic hybrid material applied in optical storage is synthesized by the sol-gel process. The photopolymeric composite used in this work is based on 3-Methacryloxypropyltrimethoxysilane (MAPTMS) as precursor , Tetraethoxysilane (TEOS) as matrix, and then formed the network structure of silicon dioxide. Fill monomer, photoinitiator into pores of the network structure, and connect organic phase with inorganic phase by coupling agent. Finally, the material is fabricated. By varying the high refractive index species(HRIS) content, we can know the effect for diffraction efficiency. The highest diffraction efficiency 84.51±6.12% is obtained when HRIS content is up to TM2.Comparing to without HRIS, the diffraction efficiency improves 40.41±3.21%.This material also has no obvious higher-order diffraction, so the maximum diffraction efficiency is +1 order. The refractive index modulation is measured by N&K analysis, and maximaum value is up to 6.59*10-2.It is higher than the value calculated by Kogelnik’s coupled wave theory. The required minimum angle offset writing multiple times grating is 2∘by measuring angular selectivity. The Zr/Si atomic ratio is 0.146 by EDS analysis of SEM. The surface relief grating (SRG) is investigated by AFM, and the actual period are greater than the theoretical period.
In this study, the 532nm laser is used to record interference fringes in the holographic storage material. Vary the thickness and refractive index of the material, and makes it meet the Bragg condition.

論文審定書 i
誌謝 ii
摘要 iii
Abstract iv
目錄 v
圖目錄 viii
表目錄 xi
第一章 緒論 1
1-1前言 1
1-2 研究動機 3
第二章 理論基礎與文獻回顧 4
2-1 全像術 4
2-1-1 全像術簡介 4
2-1-2 全像干涉 4
2-2 體積全像與薄全像之分類 7
2-3 光學性質 9
2-3-1 繞射效率計算方法 9
2-3-2 穿透率 10
2-4光聚合 10
2-4-1光啟始劑 10
2-4-2光聚合反應 12
2-4-3 光柵形成的原理 14
2-5 全像感光儲存材料 16
2-5-1 鹵化銀材料 16
2-5-2重鉻酸明膠材料 17
2-5-3光折變材料 17
2-5-4 感光高分子 18
2-5-5 高折射率物質 20
2-6溶膠-凝膠法 23
2-6-1溶膠-凝膠法之發展與簡介 23
2-6-2溶膠-凝膠法之優缺點 26
2-6-3影響溶膠-凝膠法之因素 27
第三章 材料製程與分析 31
3-1實驗藥品 31
3-2全像光儲存材料的製備 34
3-3材料光學性質分析 36
3-3-1光學實驗設備 36
3-3-2全像干涉-記錄 36
3-3-3全像干涉-讀取 37
3-4 儀器使用 38
第四章 結果與討論 41
4-1全像儲存材料的光學性質之分析 41
4-1-1 MAPTMS作為基材觀察HRIS添加量的效應 41
4-1-2 MAPTMS添加TEOS觀察HRIS添加量的效應 45
4-1-3 不同MAPTMS/TEOS比例對繞射效率影響 51
4-1-4 N&K 折射率分析 54
4-1-5 以Kogelnik’s coupled wave theory計算Δn 56
4-1-6 以旋轉塗覆spin-coating試片觀察HRIS影響 57
4-1-7 角度選擇性(Angular selectivity) 58
4-2 全像儲存材料表面形貌之分析 60
4-2-1 掃瞄式電子顯微鏡 (SEM)之表面形貌 60
4-2-2 以滴管塗覆試片觀察原子力顯微鏡(AFM)之表面形貌 62
4-2-3 以旋轉塗覆試片觀察原子力顯微鏡(AFM)之表面形貌 65
4-2-4 提升單體含量觀察原子力顯微鏡(AFM)之表面形貌 67
4-2-5 各比例之光學顯微鏡(OM)分析 69
4-3 傅立葉紅外線光譜(FT-IR)之分析 70
4-3-1 HRIS(MA與ZPO)的鉗合 70
4-3-2 HRIS添加量的影響 71
4-3-3 碳碳雙鍵(C=C)消耗率 73
4-4 探討HRIS添加過量導致最大繞射效率下降之原因 78
4-4-1 單體含量過多(以提高干涉角度來驗證) 78
4-4-2 二氧化鋯(ZrO2)晶體的生成(以XRD繞射來驗證) 81
4-4-2 Zr-O-Si鍵結的生成(以Raman光譜來驗證) 82
4-5 BET量測孔洞結構類型 83
第五章 結論 85
第六章 建議未來工作 86
參考資料 87

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