仿效自然界中無序光子晶體(amorphous photonic crystals)的特性；如緋紅金剛鸚鵡(Scarlet macaw)的藍色羽毛，乃源於藍色可見光的結構性發光，亦即當其奈米網狀材料之有序尺寸或骨幹間距與入射波長相近時，將可於特定波長具有反射性。本研究擬利用凝膠化誘導相分離(gelation-induced spinodal decomposition)，以有機三烷氧基矽烷(organotrialkoxysilane)系列之甲基三甲氧基矽烷(methyltrimethoxysilane, MTMS)作為前驅物進行溶膠凝膠法，控制其相行為可於離相分解區域，進行誘導相分離形態，製備衍生混成多孔材料，以期呈現無序光子晶體之特性。本研究發現可透過酸鹼值的改變，進行兩步驟催化反應，在合適的溫度調控下，獲得溶膠凝膠法反應之水解及縮合速率的最佳化條件；同時，可經由嵌段共聚物之添加，於反應中作為界面活性劑，達到離相分解中網狀結構之尺度的調控，隨時間的演進而有效地獲得不同尺度的(特別是奈米尺度)之網狀結構，以應用於不同波段之無序光子晶體開發。本研究的最終目的，乃是使用此奈米多孔網狀有機三烷氧基矽烷衍生混成材料薄膜，考量其於紫外光與可見光波段不吸收的特性，製備高反射(特別是深紫外光波段)之光學膜，以期應用於UVC LED 之元件開發。

Herein, we aim to develop a platform technology for the fabrication of porous organotrialkoxysilane-derived hybrids (CH3SiO1.5) through a sol-gel reaction with controlled gelation-induced phase separation. To reticulate the forming pores with controlled size, systematic examination of the sol-gel reaction of methyltrimethoxysilane (MTMS) precursors was carried out under different reaction environments. With precise pH value and temperature control for the sol-gel reaction through hydrolysis and condensation, it is feasible to acquire network-structured polymethylsilsesquioxane (PMSQ) through spinodal decomposition from gelation-induced phase separation. Consequently, a spontaneous phase separation of gels from solution during sol-gel reaction leads to the formation of co-continuous texture through morphological evolution. After removal of the residual solution, free-standing network-structured PMSQ with controlled pore size could be formed. Most importantly, the forming pore size of the reticulated porous PMSQ can be well adjusted by introducing specific polymers as surfactants. As found, with the use of poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymers (PEO-PPO-PEO), the porous PMSQ gels possess pore size ranging from tens nanometer to micrometer. The platform technology for the fabrication of a variety of porous PMSQ with pore sizes ranging from 50nm to 5μm gives rise to the appealing properties as a wide variety of applications; in particular, we are interested in the development of amorphous photonics as optical devices with angle-independent reflectance by exploiting the fabricated porous PMSQ with the pore size at different length scales.

摘要---------------------------------------------------------I
Abstract----------------------------------------------------II
Contents----------------------------------------------------IV
List of Table-----------------------------------------------VI
Figure Caption---------------------------------------------VII
Chapter 1 Introduction---------------------------------------1
1.1 Metamaterials------------------------------------------1
1.1.1 Photonic Crystals in Nature-------------------------1
1.1.2 Amorphous Photonic Crystals-------------------------4
1.2 Nanostructured Materials Fabrication-------------------7
1.2.1 Self-assembly of Block Copolymers (BCPs)------------7
1.2.2 Templated Synthesis from Bottom-up Approaches-------9
1.2.3 Templated Synthesis from Soft Template-------------11
1.2.4 Polymerization-Induced Microphase Separation-------14
1.2.5 Gelation-Induced Phase Separation------------------16
Chapter 2 Objectives----------------------------------------27
Chapter 3 Experimental--------------------------------------29
3.1 Sample Preparation------------------------------------29
3.1.1 Synthesis of PMSQ via Sol-gel Reaction-------------29
3.2 Instrumentation---------------------------------------30
3.2.1 Field-Emission Scanning Electron Microscopy (FESEM)30
3.2.2 Measurements of Trasmittance-----------------------30
3.2.3 Measurements of reflectance------------------------30
3.3 Calculation of length scales--------------------------31
3.3.1 Methodological calculation from software ImageJ----31
Chapter 4 Preliminary Results and Discussion----------------32
4.1 Sol-Gel Reaction of MTMS Precursor--------------------32
4.2 pH value Effects--------------------------------------34
4.3 Temperature Effects-----------------------------------38
4.4 Introduced Surfactant on Morphological Development----41
4.5 Molecular Weight of Surfactant Effects----------------46
4.6 Morphological evolution from Spinodal decomposition---49
4.7 Mechanisms for Gelation-Induced Phase Separation------55
4.8 Approaches for length scale tuning--------------------60
4.9 Optical Properties------------------------------------64
4.10 Reflectance Measurement of PMSQ network structure----66
Chapter 5 Conclusions and Perspectives----------------------70
Reference---------------------------------------------------72

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