New Polyimide and Poly(acrylate)/Titania HybridOptical Films

有機無機混成材料具有結合其組成物質的特性而產生新功能性材料之潛力。在混成材料中，二氧化鈦扮演著重要的奈米微粒且其擁有許多特別的光學性質，如高折射率，然而製備感光性高分子二氧化鈦混成光學膜尚待研究。在此論文中，主要在設計及合成新感光性聚醯亞胺混成二氧化鈦材料與熱交聯的壓克力高分子混成二氧化鈦材料，並探討其光學及其他物理特性。 論文首先研究探討高折射率又有光敏感性的聚醯亞胺混成二氧化鈦材料。此材料由有壓克力官能基修飾的聚醯亞胺和二氧化鈦前趨物利用酯化反應所合成出來，由羧酸和二氧化鈦的比例，酸的含量，水的多寡，混合的溶劑，等等因素控制可得均勻成一相的混成材料。且所得薄膜具有可寬廣調變的折射率範圍（n = 1.58～2.03），良好的熱性質，且在可見光區具有很高的穿透度。而且此材料可以沖洗出Y字形的圖案，其線與線的間距大約50微米。次探討熱交聯的壓克力高分子二氧化鈦混成材料，此材料乃由有壓克力官能基修飾的二氧化鈦前趨溶液和壓克力單體混成，再經由多步驟的熱交聯所製備。而所製備的混成薄膜具有的折射率範圍大約在n = 1.50～1.73。且其也具有平滑的表面和在可見光區有良好的穿透度。所研究之高分子二氧化鈦混成材料具有優良的光學特性，可在光電元件，如抗反射膜，光波導等方面具應用潛力。Organic-inorganic hybrid materials could combine the unique properties of organic and inorganic components to form new functional materials. Among hybrid materials, titania presents the important nanobuilding block and possess several unique optical properties, such as high refractive index. In this thesis, new hybrid optical films of polyimide or polyacrylate–titania hybrid materials were studied for optical applications. New high refractive index polyimide–titania hybrid materials were synthesized and characterized. A soluble polyimide grafted photosensitive methacrylate was first synthesized from 4,4’-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,5-diaminobenzoic acid (DABA), 4-aminobenzoic acid (4ABA), and 2-hydroxyethyl methacrylate. Then, the remaining COOH could undergo an esterification reaction with titanium butoxide and provide organic–inorganic bonding to obtain a homogeneous hybrid solution. Then, it was spin-cast into thin films and cured to obtain the hybrid films. These hybrid films possess a wide range of tunable refractive index (n=1.58-2.03), excellent thermal properties, and good transparency in visible range. Besides, they could be also developed to a Y-shape channel patterns with 50 line width.n the second topic of this thesis, thermal curable polyacrylate–titania hybrid materials were synthesized and characterized. First, precursor solution was prepared from methacrylate modified titania precursors and methacryalte monomer mixture. Then, the precursor solution was spin-cast to thin films and followed by multi-step theraml curing process to obtain the hybrid films. The prepared hybrid films poseess tunable and high refractive index (n=1.50-1.73), good surface uniformity and optical transparency in the visible range.中文摘要 ibstract iiable of Contents............................................................................................................iiiist of Figures vist of Tables viiihapter 1： Introduction 1-1 Introduction 1-2 Sol-gel chemistry 4-2-1 Mechanisms of hydrolysis and condensation 5-2-2 Several factors affect the rate of the sol-gel reaction 6-3 Strategies for the design of organic-inorganic hybrid materials 8-3-1 Titania based hybrid materials 10-3-2 Polyimide-titania hybrid materials 10-3-3 Poly(methyl methacrylate)-titania hybrid materials 11-3-4 Patterning of organic-inorganic hybrid materials 12-4 Research objectives 12hapter 2： Experimental 25-1 Materials 25-2 Instruments 30-3 Synthesis schemes 34-3-1 Synthesis of polyimide-titania materials and their optical thin films 34-3-2 Synthesis of polyacrylate-titania materials and optical thin films 37-4 Characterization of hybrid materials and optical thin films 38hapter 3： Synthesis, Characterization, and Photopatterning of Polyimide-Titania Optical Thin Films 49-1. Introduction 49-2 Structural characterizations of photosensitive polyimide 50-3 Structural characterizations of Polyimide-titania hybrid thin films 51-3-1 Thermal analysis 52-3-2 Surface Morphologies 53-3-3 XRD analysis 53-3-4 Optical properties 54-3-5 Patterning of polyimide-titania hybrid thin films 54-4 Conclusion 55hapter 4： Polyacrylate-Titania Hybrid Materials and Optical Thin Films 74-1. Introduction 74-2 IR analysis 74-3 Thermal analysis 75-4 Surface morphologies 75-5 Optical properties 76-6 Conclusion 77hapter 5 Conclusions 89eferences 9