摘要
高分子雙嵌段共聚合物聚苯乙烯-共-2-乙烯基吡啶 (PS-b-P2VP)所製成具有層板結構的光子晶體薄膜，透過電壓調控化學環境影響薄膜的結構，進而改變薄膜反射出來的可見光波長，可以設計成一個電致變色的裝置。透過控制溶劑退火的條件，在導電玻璃上得到大範圍規則排列且與基材平行的PS-b-P2VP層板結構，再利用季銨化修飾雙嵌段共聚合物的P2VP鏈段，增加層板結構對化學環境的響應，接著放上一個墊片分離上下電極，並注入電解液，便完成電致變色的裝置。其中三點為主要影響反色波長變化的因素，分別為季銨化化學改質薄膜的程度、施加正或負電壓以及施加電壓的強度。控制薄膜被季銨化的程度可以調控在電解液中初始的可見光波長，被季銨化程度越高的薄膜，在電解液中所呈現出來的顏色越往高波長移動;施加正或負電壓會改變電解液對薄膜的影響 ，施加正電壓會使薄膜的P2VP鏈段被電解液質子化，並被膨潤使顏色往高波長紅移，施加負電壓反而使薄膜的P2VP鏈段被電解液去質子化，並收縮使顏色往短波長藍移;施加電壓的強度影響波長的變化幅度。此外，透過利用銅網當作遮罩，並且照紫外光(254nm)交聯住被紫外光照到的部分薄膜，被光罩遮住的地方不會被交聯，且保有電致變色的效果，利用此方式可以在光子晶體上製程微米等級的圖形。電致變色的研究過程中，幸運地發現此光子晶體薄膜額外有陰離子介面活性劑感測器的應用，透過肉眼觀察光子晶體顏色的變化，得知溶液中的十二甲基磺酸鈉(SDS)的含量。此光子晶體薄膜的靈敏度相較於先前的文獻有兩到三個數量級的提升。

Abstract
Electrochemically-controlled active colour change of the thin-film photonic crystal is carried out in the lamella-structured poly (styrene-block-2-vinylpyridine) (PS-P2VP) block copolymer. With solvent annealing technique, long-range-order and highly-aligned lamellar microstructures with the lamellar normal perpendicular to the substrate were successfully prepared in the quaternized PS-P2VP thin film. We found that the electrochromic response is strongly dependent on the degree of the quaternization of the P2VP chain, the applied potential and positive or negative voltage. Because of the enhanced polar interaction by quaternization reaction, the highly-quaternized P2VP chains could lead to longer-wavelength reflectance of the PS-b-QP2VP thin film in the electrolyte. The larger applied positive voltage on the thin film side could result in significant red-shifting reflectance due to the swelling and expansion of the layered QP2VP microdomain, whereas the larger applied negative voltage (absolute value) on the thin film side could give rise to inversely blue-shifting reflectance due to the deswelling and contraction of the QP2VP microdomain. In addition, this electrochromism can be also observed in the PS-b-QP2VP thin film having a well-defined patterned texture generated by a mask irradiated by ultraviolet light. More interestingly, a specific highly-sensitive detection to a surfactant of sodium dodecyl sulfate (SDS) is found using the PS-b-QP2VP photonic crystal thin film. With different degree of the anion exchange with the Br- on the QP2VP chain, blue- and red-shifting structural coloration by the QP2VP layers in the extremely low and high SDS concentration can be directly observed by naked eyes, respectively. As compared to the previous report, the minimum sensitivity for SDS concentration has a great progress at least one order by using this PS-b-QP2VP photonic crystal as a photonic detector.

Contents
論文審定書 ....................................................................................................................... i
誌謝 .................................................................................................................................. ii
摘要 ................................................................................................................................. iii
Abstract .......................................................................................................................... iv
Contents ........................................................................................................................... v
List of Figures ............................................................................................................... vii
List of Tables ................................................................................................................ xvi
Chapter 1. Introduction 1
1.1 Block Copolymer (BCP) Self-assembly 1
1.2 Photonic Crystals 3
1.2.1 Fabrication of Photonic Crystals from BCP self-assembly 6
1.2.2 Stimuli-Responded BCP Photonic Crystals 9
1.3 Control of Optical Reflectivity of BCP Photonic Crystals 12
1.4 Applications of Photonic crystal 16
1.4.1 Electro Chemically Tunable BCP Full Color Pixels 16
1.4.2 Ions Sensing 21
1.4.3 Broad-Wavelength-Range Chemically Tunable BCP Photonic Gels 22
1.4.4 Photonic Crystal Surfactant Detection 26
Chapter 2. Objectives 29
Chapter 3. Materials and Experimental Methods 30
3.1 Materials 30
3.2 Sample Preparation 30
3.2.1 Bulks Samples Preparation 30
3.2.2 Thin Film Samples Preparation 31
3.3 Microstructural Characterization 31
3.3.1 Transmission Electron Microscopy (TEM) 31
3.3.2 Ultra-small Angle X-ray Scattering (USAXS) 32
3.3.3 Fourier Transform Infrared (FTIR) Spectroscopy 32
3.3.4 Ultraviolet–Visible Absorption Spectroscopy 33
3.3.5 Electrochromic device 33
Chapter 4. Results and Discussion 34
4.1 Microphase Separation of PS-b-P2VP BCPs in Bulk. 34
4.2 Microphase Separation of PS-b-P2VP BCPs in Thin Film. 35
4.2.1 Thin Film Morphologies 35
4.2.2. Control of Microstructural Orientation by Solvent Annealing 36
4.3 Optical Properties of PS-b-P2VP Photonic Crystal Thin Films 40
4.4 Electrochromic Properties of Lamella-Structured Photonic Crystal Thin Films 42
4.4.1 Electrochromism of Lamella-Structured PS-b-P2VP Photonic Thin Films 43
4.4.2 Electrochromism of 72h-Quaternized PS-b-P2VP Photonic Crystal Thin Films 46
4.4.3 Electrochromism by Alternating Positive or Negative Voltage 48
4.4.4 Electrochromism of Photopatterned Photonic Thin Film 50
4.5 Photonic Crystal Thin Film for Sensing Surfactants 52
4.5.1 Optical Properties of PS-b-QP2VP in Surfactants 52
Chapter 5. Conclusion 64
Chapter 6. References 66

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