由高度可撓性、可大面積量產等優點的自組裝嵌段共聚物所製備的近紅外光
光子晶體在光傳輸、雷射共振腔、感測器、防偽標籤、節能等應用近年備受矚目。
然而，受到共聚物相分離結構尺寸及其有序性的侷限，卻難以利用單一分子量達成
橫跨可見光至短波紅外光波段能隙之條件。在此文中，我們介紹了一種新技術能夠
克服嵌段共聚物高分子的尺度局限性，而獲得有序的微結構，使薄膜成為能夠反射
某特定波段之固態光子晶體。利用此技術首次在高分子自組裝領域達到橫跨近紅
外光波段的固態光子晶體能隙。

Large-area and flexible photonic crystals by self-assembly of copolymers with
tunable forbidden bandgaps in near infrared are expected to be very critical in advanced
applications of optical communication, laser cavity, sensing field, anti-counterfeit label,
energy conservation and so on. However, accomplishment of the requirement mentioned
above is extremely tough for a single-molecular-weight copolymer due to the limitations
of the lattice spacing and orientational control of the microphase-separated structure. Here,
we established a unique technique by which periodic microscale structures are
spontaneously constructed. Consequently, without the need of altering molecular weights,
the photonic bandgaps could easily be extended to infrared regime in solid state.

論文審定書....................................................................................................................... i
致謝.................................................................................................................................. ii
摘要................................................................................................................................. iii
Abstract .......................................................................................................................... iv
Content ............................................................................................................................ v
List of Figures ............................................................................................................... vii
List of Tables................................................................................................................. xii
Chapter 1. Introduction ................................................................................................. 1
1.1 Photonic Crystals............................................................................................. 1
1.2 Block Copolymer (BCP) Self-assembly......................................................... 3
1.3 Self-Assembly of Copolymer/ Liquid Crystal Composites.......................... 6
1.4 BCP Photonic Crystals ................................................................................... 9
1.5 Ultra-High-Mw Brush BCPs........................................................................ 16
1.5 Solvent-Induced Collective Osmotic Shock (COS) .................................... 19
Chapter 2. Objective .................................................................................................... 26
Chapter 3. Materials and Experimental Methods..................................................... 27
3.1 Materials ........................................................................................................ 27
3.2 Sample Preparation....................................................................................... 28
3.2.1 Thin Film Samples Preparation ...................................................... 28
3.2.2 Ternary Blends of PS-P2VP, PS, and Additive Organic Molecules
..................................................................................................................... 28
3.2.3 Nanonetworks-Triggered Microlayers (NNTML)......................... 28
3.2.4 TiO2 Infiltration ................................................................................ 29
3.3 Microstructural Characterization ............................................................... 29
3.3.1 Transmission Electron Microscopy (TEM).................................... 29
3.3.2 Field Emission Scanning Electron Microscopy (FESEM) ............ 30
3.3.3 Small Angle X-ray Scattering (SAXS) ............................................ 30
3.3.4 Reflectivity Measurements............................................................... 31
4.1 Nanonetworks-Triggered Microlayers (NNTML) ..................................... 32
4.2 Ultrabroad Photonic Bandgaps of NNTML-Containing Films................ 38
4.3 Optical Properties of PS(PSh)-P2VP(Chol)x Based Photonic Crystals..... 44
4.3 Theory of Osmotic-Stress-Controlled NNTML.......................................... 49
4.3 Extremely-Wide Range Reflection Bands Accessed by Alternating
Additives............................................................................................................... 52
Chapter 5. Conclusion.................................................................................................. 60
Chapter 6. Reference.................................................................................................... 61

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