本研究擬利用聚苯乙烯-聚二甲基矽氧烷嵌段共聚物 (polystyrene-b-polydimethylsiloxane)，進行自組裝結合模板化製程，製備高有序及無序光子晶體。首先利用拉伸塗佈法，進行嵌段共聚物奈米網狀薄膜之製備，再經由溶劑退火的方式，以獲得不同有序程度的奈米網狀薄膜，之後以氫氟酸分解含矽鏈段，獲得奈米多孔聚苯乙烯，以此多孔材料為模板，進行模板化溶凝膠法，移除模板後即可成功製備奈米網狀金屬氧化物。仿效自然，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，將可呈現如蝴蝶翅膀之結構性發光的光子晶體特性，於特定波長具有反射性。此結構性發光與奈米網狀結構之有序程度有關，具有高有序程度的網狀材料，將呈現高反射但與其反射性與入射角相依，對於相對無序(短程有序)的網狀材料，雖反射強度減弱但其反射性將與入射角無關。若此尺寸與間距遠小於其入射波長時，則將呈現光學超穎材料的特性，可達到高穿透之光學特性。本實驗的最終目的，乃是使用此奈米網狀陶瓷氧化物薄膜，以期在紫外光波段不吸收的前提下，製備紫外光波段高反射與高穿透之光學膜。

In this study, we aim to fabricate photonic (well-ordered) crystals and amorphous photonic (short-range-order) crystals with UVC responsive wavelength from the self-assembly of polystyrene-b-poly (dimethylsiloxane) (PS-PDMS) followed by templated syntheses, including templated sol-gel and crosslinking reactions. Nanonetwork-structured films with controlled ordering were obtained from the self-assembly of PS-PDMS by dip coating process followed by solvent annealing. With the morphological evolution during solvent annealing, nanonetwork phases with increasing ordering could be developed. Subsequently, hydrofluoric (HF) acid was used to etch the PDMS, giving the nanoporous PS as a template for templated syntheses, in particular for sol-gel reaction of ceramic oxide precursors. Biomimicking from nature, the forming nanonetwork material is expected to give structural coloration with high reflectance while the interdomain spacing is equivalent to the responsive wavelength. Most interestingly, the appearing optical properties were found to be strongly dependent on the degree of structural order for the forming networks. In contrast to the well-ordered networks from the butterfly wing structure with high reflectance but angle dependent, amorphous photonic crystals with partially ordered texture is expected to give unique optical behaviors with angle independence. Furthermore, the nanonetwork materials fabricated with interdomain spacing smaller than the responsive wavelength was found to give high transmittance with the characters of optical metamaterials. The final goal is to exploit the nanonetwork films fabricated as optical films for high reflectance and transmittance materials, in particular, in the applications of UVC optical devices.

摘要........................................................... I
Abstract....................................................... II
Contents....................................................... IV
Figure Caption................................................. VI
Chapter 1. Introduction........................................ 1
1.1 Metamaterials.............................................. 1
1.1.1 Photonic crystals in nature...................... 1
1.1.2 Amorphous photonic crystals...................... 4
1.1.3 Subwavelength properties......................... 6
1.2 Nanonetwork phases......................................... 8
1.2.1 Nanostructures of gyroid phase........................... 8
1.2.2 Nanostructures of diamond phase.......................... 12
1.3 Self-assembly.............................................. 13
1.3.1 Self-assembly of block copolymers (BCPs)................. 14
1.3.2 Self-assembly of silicon-containing BCPs................. 15
1.3.3 Fabrication of BCP thin films............................ 18
1.4 Templated synthesis........................................ 20
1.4.1 Bottom-up approaches for nanomaterials................... 22
1.4.2 Nanoporous templates from degradable block copolymers.... 23
1.4.3 Templated syntheses for nanonetwork materials............ 28
Chapter 2. Objectives.......................................... 30
Chapter 3. Experimental........................................ 32
3.1 Synthesis of PS-PDMS BCPs.................................. 32
3.2 Sample preparation......................................... 34
3.2.1 Solution casting for nanonetwork phases.................. 34
3.2.2 Dip coating for nanonetwork thin films................... 35
3.2.3 Fabrication of nanoporous templates...................... 36
3.3 Templated synthesis of nanonetwork SiO2.................... 36
3.4 Templated synthesis of nanonetwork chitosan................ 37
3.5 Removal of the PS template................................. 37
3.6 Instrumentation............................................ 38
Chapter 4. Results and Discussion.............................. 40
4.1 PS-PDMS thin films with nanonetwork textures............... 40
4.1.1 Nanonetwork bulk from solution casting................... 40
4.1.2 Nanonetwork thin films from dip coating.................. 44
4.1.3 Morphological evolution from thermal annealing........... 47
4.1.4 Morphological evolution from solvent annealing........... 50
4.2 Large Mn PS-PDMS films with nanonetwork textures........... 56
4.2.1 Nanonetwork bulk from solution casting................... 56
4.2.2 Morphological evolution from solvent annealing........... 58
4.3 Templated synthesis of nanonetwork materials............... 61
4.3.1 Nanoporous PS template from etched PS-PDMS............... 61
4.3.2 Templated sol-gel reaction for nanonetwork SiO2.......... 62
4.3.3 Templated crosslinking reaction for nanonetwork chitosan. 68
4.4 Measurements of optical properties in UVC regions.......... 72
4.4 Measurements of optical properties in UVC regions.......... 72
4.4.1 Low absorption materials................................. 72
4.4.2 Optical properties of nanonetwork materials.............. 75
Chapter 5. Conclusions......................................... 79
Chapter 6. References.......................................... 81

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