臺灣博碩士論文加值系統

在文獻中，蝴蝶翅膀中，高聯結性的螺旋二十四面體奈米結構可形成光子晶體並表現出特殊的光學性質。可惜的事，人造的可見光螺旋二十四面體光子晶體直到現在不易利用自組裝的方式被製造出來。
在我們的研究中，我們首先發展出利用物理方式－捕捉結構色彩方式(TOSC)－經由先澎潤螺旋二十四面體奈米結構達到可見光波長，並進一步捕捉於特定尺度下，成功的製備可見光螺旋二十四面體光子晶體薄膜於固態環境中。並且利用控制溶劑揮發的擴散距離與時間，不必經由額外添加物，只利用單一分子量嵌段共聚物高分子，聚苯乙烯接聚二乙烯吡啶(PS-P2VP)，達成調控不同的結構色彩波長與性質。利用此方法，可以有效的克服製備螺旋二十四面體光子晶體所面臨的問題。當如果要製備更長波長的螺旋二十四面體光子晶體時，我們可以導入均聚物，聚苯乙和聚二乙烯吡啶的三項混摻方式，去有效的增加我們的螺旋二十四面體中的尺度大小。進一步再利用捕捉結構色彩方式，可以使我們的螺旋二十四面體光子晶體的結構色彩，由紫外光波段到可見光波段，甚至到短波長紅外光波段，形成一個廣域波長的光子晶體材料。最後，利用溶劑揮發動力學控制，三維的高聯結性螺旋二十四面體奈米結構的排列規則可以從有序的二十四面體結構轉變為短程有序的雙連續相奈米結構，並具備有無序型光子晶體的性質；有序型的螺旋二十四面體光子晶體的光學性質會隨著角度有不同的改變，相反的短程有序的雙連續光子晶體卻不會隨著角度不同而有光學性質的改變。並且利用短程有序的雙連續的無序光子晶體，利用三相混摻的方式，也可以有效調控光學波長從可見光到紅外光波段。利用捕捉結構色彩方式，可以有效使高連續性的三維奈米維結構得到可調性的結構色彩，從短波長的紫外光到長波長的短波長紅外光，且具備相當大的淺力在於光電通訊，顯示技術，環境感測方面的應用。

In theory, gyroid photonic crystals (PCs) in butterfly wings exhibit advanced optical properties as a result of their highly interconnected microstructures. Because of the difficulties in synthesizing artificial gyroid materials having periodicity corresponding to visible wavelengths, human-made visible gyroid PCs are still unachievable by self-assembly. In this study, we first develop a physical approach—trapping of structural coloration (TOSC)—through which the visible structural coloration of an expanded gyroid lattice in a solvated state can be preserved in the solid state, thereby allowing the fabrication of visible-wavelength gyroid photonic crystals. Through control over the diffusivity and diffusive distance for solvent evaporation, the single-molecular-weight gyroid-structured polystyrene-block-poly(2-vinylpyridine) (PS-P2VP) block copolymer PC can exhibit desired structural coloration in the solid state without the need to introduce any additives. This finding of TOSC breaks through the bottleneck of the limited lattice size of the gyroid phase such that a human-made solid gyroid PC featuring tunable and switchable structural colorations was first-time fabricated by self-assembly. To enlarge the unit lattice size of the gyroid phase for acquiring longer-wavelength reflectivity, the gyroid-structured PS-P2VP/PS/P2VP ternary-blend films were prepared. By TOSC associated with controlled diffusive distances, the reflectance wavelengths of the solid-state ternary-blend PC films could be exceedingly extended from ultraviolet (UV) to visible (Vis) to near infrared (NIR) and even to short-wavelength infrared (SWIR) range. In addition, with the controllable degree of orderedness of three-dimensional (3-D) network microstructures by a solvent-evaporation-driven method, typical PCs or amorphous photonic crystals (APCs) featuring angle-dependent or angle-independent structural colorations could be accomplished. With the increase of vapor pressure of neutral solvents for spin-casting, network morphologies with gradually decreased microstructural orderedness from well-order gyroid to low-order gyroid to short-range-order bicontinuous to disorder microstructures could be obtained sequentially. By expansion of the unit lattice size of the network microstructure, lengthening the angle-independent structural coloration from UV to NIR range was observed in PS-P2VP APC films after TOSC treatment. This provides an efficient way to rapidly control microstructural orderedness of network morphologies to fabricate human-made PCs or APCs featuring tunable structural colorations. As a result, with this novel TOSC technique, 3-D periodic network microstructures could exhibit scalable photonic band gaps ranging over UV to SWIR wavelength range, being promising in the applications of optical communication, laser cavity, wave guide, display and recognition devices.

論文審定書 ⅰ
論文公開授權書 ⅱ
致謝 iii
摘要 iv
Abstract v
Table of Contents vii
List of Tables x
List of Figures xi
Chapter 1. Introduction 1
1.1 Photonic Crystal in Nature 1
1.2 Human-made Photonic crystal 6
1.2.1 1D and 2D Block Copolymer Photonic Crystals 15
1.2.2 3D Photonic Crystal 25
1.3 Amorphous Photonic Crystals in Nature 29
1.3.1 Artificial Amorphous Photonic Crystals 31
Chapter 2. Objectives 38
Chapter 3. Materials and Experimental Methods 40
3.1 Materials 40
3.2 Sample Preparation 40
3.2.1 Bulks Samples Preparation 40
3.2.2 Thin Film Samples Preparation 41
3.2.3 Ternary Blend with BCP 42
3.3 Trapping of Structural Coloration 42
3.4 Microstructural Characterization 43
3.4.1 Transmission Electron Microscopy (TEM) 43
3.4.2 X-ray Experiments of Small Angle X-ray Scattering (SAXS) 43
3.4.3 Field Emission Scanning Electron Microscope 44
3.4.4 Reflectivity Measurement 44
3.4.5 Scanning Probe Microscopy 44
3.4.6 Water Contact Angle Measurements 45
Chapter 4. Results and Discussion 46
4.1 Self-assembled Morphologies of PS-P2VP BCPs in Bulk 46
4.2 Film Morphologies of PS-P2VP BCPs 47
4.2.1 Morphologies of As-Spun Films 47
4.2.2 Phase Transition Driven by Solvent Annealing Method 57
4.3 PS-P2VP Photonic Crystal Films with Different Shapes of Microstructures 68
4.3.1 Lamellar Photonic Crystal Film 68
4.3.2 Trapping of Structural Coloration by a Bioinspired Gyroid-Structured Photonic Crystal 70
4.3.3 Tunable Visible Structural Coloration by Evapochromism 91
4.3.4 Detection of Alcohols Using Gyroid-Structured Photonic Crystals 93
4.3.5 HPL-Structured Photonic Crystals 96
4.4 Solid-State Gyroid Photonic Crystals with Scalable Reflectance Wavelength 98
4.4.1 TOSC Using Low-Order Gyroid Microstructures 98
4.4.2 4.4.2 Vis to NIR Reflectance Wavelengths in Ternary-Blend Films 99
4.4.3 Solid Gyroid Photonic Crystals Featuring SWIR Reflection 105
4.5 Network Photonic Crystals with Tunable Iridescent or Noniridescent Structural Colors 110
4.5.1 Solvent-Evaporation-Controlled Ordering Degree of 3-D Network Microstructures. 110
4.5.2 Structural Colorations of Network Photonic Crystal Films with Various Ordering Degrees. 115
4.5.3 Block Copolymer APCs with Tunable Noniridescent Colors from UV to NIR. 119
Chapter 5. Conclusion 127
Chapter 6. Reference 129
Resume 143
 
List of Tables
Table 3-1 Characterization of PS-P2VP BCPs 40
Table 4-1 Polymer-solvent interaction parameters 49
Table 4-2 Parameters of gyroid-structured photonic crystal films 105
Table 4-3 Polymer-solvent interaction parameters 112




















List of Figures
Figure 1-1. Photonic Crystals with various periodic structures found in natural creatures. (a) Plant flowers with one-dimensional (1D) stacking layers, such as Hibiscus trionum and Tulipa species. (b) One-dimensional multilayers of bugs. (c) Gradient 1D periodicity in Morpho butterflies. (d) Natural surfaces with 2D gratings are used for antireflection and self-cleaning by some nocturnal insects, such as moth and some butterflies. (e) Natural 2D periodicity in the form of cylindrical voids that are embedded in a high-refractive-index solid medium, such as those found in the iridescent hairs of certain marine worms—Aphrodite. (f) Close-packed spheres of solid materials generate the iridescence of gem opals and have recently been discovered in the beetles—Pachyrhynchus argus. (g) Inverse opal analogous nanostructures generate the iridescence of several species of exotic butterflies, such as the Parides sesostris. 2
Figure 1-2. (a) SEM micrograph of wing scale of P. sesostris. (b) TEM micrograph of C. rubi. 6
Figure 1-3 SAXS profiles of Teinopalpus imperialis, Paridessesostris, Callophrys (Mitoura) gryneus, Callophrys dumetorum, and Cyanophrys herodotus. The vertical lines correspond to the expected Bragg peak positional ratios for the single gyroid space group (I4132) 6
Figure 1-4 (a) The 2D photonic band diagram of a typical polymeric solid having a permittivity of ɛ=2.6ɛ0with embedded air cylinders in a square lattice. The air cylinders have a radius r=0.45a , where a is the lattice constant of the structure (inset). The partial PBG for TE-polarization is shown in red for the Γ−X and the Γ−M directions, respectively. (b) The 2D photonic band diagram of the same structure with a higher permittivity of ɛ=13ɛ0 exhibiting a PBG for TM-polarized waves and for TE-polarized waves. However, since the TE and TM gaps do not overlap, there is no polarization-independent complete gap. (c) The 2D photonic band diagram in (b) is folded along the boundary of the irreducible BZ. 10
Figure 1-5 (a) A side-view SEM image of the released five-layered structures of photonic crystals.38 (b) A polymeric photonic crystal generated by exposure of a 10-μm photoresist film to the interference pattern. Scale bar is 10μm. 11
Figure 1-6. (a) Transmission spectra represented the relation between temperature and reflectance peak in colloidal photonic crystals featuring 415 nm nanoparticles. (b) SEM images of a sample treated at T = 950 °C (a, b, and c) and at T= 1050 °C (d, e, and f). Different types of internal FCC crystalline facets obtained after cleavage are shown {111} (a and d), {100} (b and e), and {111} terraces (c and f). 13
Figure 1-7. (a) Photographs of colloidal photonic crystals formed in response to an external magnetic field. (b) Reflection spectra at normal incidence of the colloidal photonic crystals, varied with the distance of the sample from the magnet. Diffraction peaks blue-shift (from right to left) as the distance decreases from 3.7 to 2.0 cm.
14
Figure 1-8. Schematic phase diagram showing the various ‘classical’ BCP morphologies adopted by non-crystalline linear diblock copolymer. The blue component represents the minority phase and the matrix, majority phase surrounds it. 17
Figure 1-9 (a) Back scattering electron image (BEI) of a fracture surface of a PS-PI block copolymer containing 40% homopolymers. After stained with OsO4, bright regions are PI and dark regions are PS. (b) Reflectivity profile of the blend samples containing 5%, 20%, 40%, and 50% of total added homopolymers 18
Figure 1-10 (a) Schematic diagram of the lamellar structure of the PS-P2VP photonic crystal gel film and the corresponding tuning mechanism for various structural colors. (b) Ultraviolet–visible–near-infrared absorbance spectra of lamellar photonic gels swollen by immersing in NH4Cl aqueous solutions with different concentrations. (c) Photograph of the photonic gel film when immersed in water. 19
Figure 1-11 (a) Cephalopods displays the manipulate light by changing the spacing of the lamellae. (b) Chemical tunability of the spacing and the refractive index of the gel layers in the PS-P2VP BCP. 21
Figure 1-12 (a) Normal incidence optical images and (b) experimental reflectivity spectra of IL-swollen photonic films of blends of PS-P2VP-1 and PS-P2VP-3. Both images and spectra are displayed in the order of the amount of PS-P2VP-3 added from left to right, i.e., PS-P2VP-1/IL, 3:1 (PS-P2VP-1:PS-P2VP-3)/IL, 1:1 (PS-P2VP-1:PS-P2VP-3)/IL, 1:3 (PS-P2VP-1:PS-P2VP-3)/IL, and PS-P2VP-3/IL.
21
Figure 1-13. (a) Illustrations of the PS-P2VP film quaternized with 2-(bromomethyl) phenylboronic acid and of the boronic acid binding D-fructose. (b) The quaternized PS-P2VP film can detect sugars in aqueous solution or the phosphate buffered saline by red shifting of reflectance wavelength. Pictures of films exposed to different concentrations of D-fructose in deionized water. As exposure to (c) deionized water, the film displayed a blue color. Exposure to (d) 500 μM, (e) 5 mM and (f) 50 mM, resulted in a turquoise, green and orange color, respectively. 23
Figure 1-14 (a) Cross-sectional AFM phase image of the PS microdomains viewed parallel to the cylinder axis. PS is white in the image. (b) The optical graph of a roll-cast PS-PI BCP film on a steel roller. (c) Transmission (dot curve) and reflectance (solid curve) spectra of the roll cast film measured with normal incident unpolarized light. Reflectance spectrum shows a strong reflectance over the wavelength range of 390–440 nm. The film showed almost zero transmission at the wavelength of maximum reflectance. 24
Figure 1-15. The complete photonic band gap of single network members such as (a) single gyroid, (b) single diamond and (c) single primitive. (d) The partial photonic band gap appeared in a double gyroid lattice. 26
Figure 1-16. (a) TEM micrograph of the double gyroid PS-PI BCP. After stained with OsO4, PS is bright and PI is dark. (b) SEM micrograph of ozone-etched fractured PS-PI bulk film. 29
Figure 1-17. Cross-sectional micrographs of APCs found in the biological world. (a) TEM micrograph of collagen arrays in the lightblue-colored caruncle of the asity N. coruscans (lower left corner). Inset (upper right) shows the corresponding Fourier power spectrum. (b) TEM of a feather barb of the male plum-throated cotinga (lower left corner). (c) TEM of a feather barb of the male eastern bluebird (lower left corner). Insets (upper right corner) in b) and c) show the SAXS spectra. (d) SEM micrograph of a green scale of the longhorn beetle A. graafi (lower left corner). (e) TEM of a scale of the longhorn beetle S. mirabilis (lower left corner). (f) SEM of a blue feather barb of the scarlet macaw. Inset (lower left corner) shows micrograph of the feathers. 31
Figure 1-18. (a) A series of particle suspensions with different polymer contents viewed at different title angles. (b) Reflectance wavelengths varied with titling angles in the particle suspensions with different polymer contents. 33
Figure 1-19. (a) The reflectivity intensity can be enhanced by increased film thickness. (b) The black background can eliminate the incoherent scattering. 34
Figure 1-20. (a) SEM image of colloidal glasses of bi-dispersed hollow silica particles with same cores (180 nm) but different shell sizes. (b) Cross-sectional SEM image of composites of inverse colloidal glasses consisting of TMPEOTA infiltrating between the hollow spheres. (c) Photographs of inverse colloidal glass films taken at 0° and 45° viewing angles. The reflection spectra at various viewing angles ranging from 0° to 60°. 36
Figure 1-21. (a) A scheme describing the method of synthesizing silica-coated melanin nanoparticles. (b) TEM images of core-shell syntheticmelanin nanoparticles (CS-SMNPs): 160/0, 160/36, and 160/66 nm, respectively. The red dashed circles represent the boundary of the core and shell. Scale bars, 100 nm. (c) Optical images of supraballs made of four types of nanoparticles: 224-nm pure silica nanoparticles and 160/0-, 160/36-, and 160/66-nm CS-SMNPs. Scale bars, 0.5 mm. (d) Angle-resolved spectra for olive inks. 37
Figure 4-1. TEM micrograph of the as-cast PS440-P2VP353 (fPSv=0.58) from DCM (10wt%). After I2 staining, PS is bright and P2VP is dark. 47
Figure 4-2. (a) TEM micrograph of the as-cast PS248-P2VP195 (fPSv=0.58) from DCM (10wt%). (b) The corresponding 1D SAXS profile of the PS248-P2VP195 bulk sample 47
Figure 4-3. TEM micrographs of the as-spun PS440-P2VP353 (fPSv=0.58) films from (a) PGMEA, (b) THF, (c) chlorobenzene and (d) MEK. 51
Figure 4-4. Cross-sectional TEM micrographs of the as-spun PS440-P2VP353 (fPSv=0.58) films from (a) chloroform, (c) DCE and (b) TCE. 52
Figure 4-5. Cross-sectional TEM micrographs of the as-spun PS248-P2VP195 (fPSv=0.58) films from (a) PGMEA, (b) THF, (c) chlorobenzene and (d) MEK. 54
Figure 4-6. Cross-sectional TEM micrograph of the as-spun PS248-P2VP195 (fPSv=0.58) films from DMF. 54
Figure 4-7. Cross-sectional TEM micrographs of the as-spun PS248-P2VP195 (fPSv=0.58) films from (a) chloroform, (b) DCE and (c) TCE. 56
Figure 4-8. The SAXS profile of the as-spun PS248-P2VP195 film from TCE exhibits characteristic reflections of the double gyroid phase at relative q* ratios of √6 ∶ √8: √14. 57
Figure 4-9. Cross-sectional TEM micrographs of the (a) PS440-P2VP353 (fPSv=0.58) and (b) PS248-P2VP195 (fPSv=0.58) films after solvent annealing by chloroform vapor at 50oC for 24 h. 58
Figure 4-10. Cross-sectional TEM micrographs of the PS248-P2VP195 (fPSv=0.58) films after solvent annealing by toluene for (a) 2 h and (b) 4 h at 50oC. 59
Figure 4-11. Cross-sectional TEM micrograph of the PS248-P2VP195 (fPSv=0.58) film after solvent annealing by TCE for 2 h at 50 oC. 60
Figure 4-12. Cross-sectional TEM micrograph of the PS248-P2VP195 (fPSv=0.58) film after solvent annealing by TCE for 0.5h at 50oC. 61
Figure 4-13. The corresponding SAXS profile of the PS248-P2VP195 film after solvent annealing by TCE at 25ºC for 0.5 h. The significant reflections at relative q* ratios of √6 ∶ √8: √14 indicate the formation of the gyroid microstructure. 62
Figure 4-14. Cross-sectional TEM micrograph of the PS248-P2VP195 (fPSv=0.58) film after solvent annealing by chloroform at 50oC for 2 h. 63
Figure 4-15. Cross-sectional TEM micrograph of the PS248-P2VP195 (fPSv=0.58) films after solvent annealing by chloroform vapor for 30 min at 50oC. 64
Figure 4-16. Cross-sectional TEM micrographs of the PS248-P2VP195 (fPSv=0.58) films after solvent annealing by chloroform/ethanol for 180 min at 50oC. 65
Figure 4-17. Cross-sectional TEM micrographs for the PS248-P2VP195 (fPSv=0.58) films spun-cast from chloroform and then annealed by TCE for (a) 2 h and (b) 1 h. (c) Illustration of the HPL microstructure in the PS248-P2VP195 film. 67
Figure 4-18. (a) UV–Vis spectra of the lamella-structured PS-P2VP film in ethanol (dashed line) and after complete evaporation of the ethanol (solid line). (b) Cross-sectional TEM micrograph of the lamella-structured PS-P2VP film after complete evaporation of the ethanol. Inserts are the corresponding optical photographs taken in the solvated and dried states. 69
Figure 4-19. Schematic representation of the TOSC process for fabrication of a solid gyroid PS-P2VP photonic crystal film exhibiting the visible-wavelength structural coloration. (a) The initial gyroid-structured film is colorless (i.e., provides a featureless optical image) because of its small gyroid unit lattice with respect to visible wavelengths. (b) After immersing in ethanol, the solvated gyroid-structured film exhibits red structural coloration (i.e., a human-made gyroid-structured butterfly with red structural coloration in ethanol) as a result of expansion of the gyroid unit lattice. After complete evaporation of ethanol, instead of reverting to the initial colorless state (a), the solid gyroid-structured film still displays the visible structural coloration (i.e., a butterfly with green structural coloration in the solid state) with a slight blue shift in comparison with state (b). The structural coloration in the solid (c) is attributed to immobilization of the expanded gyroid lattice in (b) during evaporation of the ethanol. Removal of the ethanol also drives the formation of porous gyroid nanochannels in (c), resulting in strong reflectivity in contrast to that in the solvated state (b). After heating the material in state (c) at 110°C, the green structural coloration disappears, due to reversion of the gyroid lattice size to that in the initial state (a), exhibiting reversible and rapid structurally color changes. 73
Figure 4-20. (a) FESEM micrograph of the green-colored wing scale of Teinopalpus imperialis (red circle). 74
Figure 4-21. The UV-Vis spectrum of the PS248-P2VP195 film. The peak at 298 nm is due to the photonic reflectance of the gyroid microstructure. Notably, the peak at 262 nm is attributed to the absorption of the PS and P2VP. 76
Figure 4-22. (a) UV–Vis spectra of the gyroid-structured PS-P2VP film in ethanol (dashed line) and after complete evaporation of the ethanol (solid line). (b) Cross-sectional TEM micrograph of the gyroid-structured PS-P2VP film after complete evaporation of the ethanol. The inset is taken under high magnification. 79
Figure 4-23. The reflectivity spectra of the TOSC-featured gyroid photonic crystal film measured at different angles. 80
Figure 4-24. (a) Schematic representation of the TOSC mechanism involving the expansion and contraction of the gyroid lattice accompanied by a series of conformational changes of the P2VP chains in the as-prepared initial film, the solvated gel film in ethanol, and the dried solid film after complete removal of the ethanol. The black and blue lines represent P2VP and PS chains, respectively. SPM images of the surface morphologies of the PS-P2VP film (b) before and (c) after TOSC treatment. The gyroid microstructure is not evident in (c) after TOSC treatment because of the coverage of a glassy P2VP layer. (d) FESEM micrograph of the sample in (c) after removal of the surficial P2VP layer by RIE, revealing the porous gyroid microstructure. (e) FESEM micrograph of the sample in (b) after RIE treatment identical to that in (d), revealing a featureless morphology. Insets: Corresponding optical photographs, indicating the identical structural coloration of the TOSC-featured PS-P2VP film before and after RIE treatment. 84
Figure 4-25. Water contact angle (WCA) measurements for the (a) neat P2VP film and PS-P2VP film (b) before and (c) after TOSC treatment. The neat P2VP film shows the WCA of 67 º. The PS-P2VP film before and after TOSC treatment reveals the WCA of 88º and 56º, respectively. 85
Figure 4-26. The cross-sectional FESEM micrographs of the TOSC-featured PS-P2VP films (a) before and (b) after thermal treatment. The films were fractured under liquid nitrogen to minimize the distortion of the lateral surfaces. (a) Nanoporous gyroid structures can be observed in the TOSC-featured film with the film thickness of 2.4 μm. (b) After heating (a) at 110 ºC for 30s (over both the Tgs of the PS and P2VP), the featureless morphology accompanied with the shrinkage of film thickness to 1.6 μm is observed. 87
Figure 4-27. Differential scanning calorimetry (DSC) profile of the PS-P2VP BCP film. The heating rate is 10 ºC/min. 88
Figure 4-28. (a) Results of 10 cycles of entrapment and reversal of structural coloration in the gyroid-structured PS-P2VP film. The visible structural coloration driven by trapping of structural coloration (TOSC) can be erased by heating the film at 110°C for 30s. (b) Optical micrographs of the bending of a gyroid-structured photonic crystal film featuring a butterfly contour on a soft and transparent poly(ethylene terephthalate) (PET) substrate. 88
Figure 4-29. Time-resolved UV-Vis spectra of the TOSC-featured PS248-P2VP195 (fPSv=0.58) film during the fuming process by ethanol vapor. 90
Figure 4-30. Cross-sectional TEM micrograph of the TOSC-featured PS248-P2VP195 (fPSv=0.58) film after solvent annealing by ethanol vapor for 5 second. 90
Figure 4-31. UV–Vis spectra of the TOSC-featured gyroid photonic crystals film (a) having a thickness of 1.6 µm after evaporation of ethanol at various temperatures and (b) of various thicknesses (0.6, 0.8, 1.6, 2.4, and 3.2 µm) after evaporation of ethanol at 25 °C. (c) Variations in reflectance peak wavelength plotted with respect to the film thickness and evaporation temperature in the TOSC-featured gyroid photonic crystal films. (d) The corresponding CIE diagram. 93
Figure 4-32. The UV-Vis spectra of the gyroid-structured PS248-P2VP195 film after TOSC treatments using methanol, ethanol and 2-propanol as solvents. 95
Figure 4-33. FTIR spectra of the gyroid BCP films after evaporation from different alcohols. 95
Figure 4-34. (a) Photograph of the HPL-structured PS248-P2VP195 (fPSv=0.58) film prior to TOSC treatment and after TOSC treatment. (b) UV-Vis spectrum of the PS248-P2VP195 (fPSv=0.58) film after TOSC treatment. 97
Figure 4-35. (a) Cross-sectional TEM micrograph of the low-order gyroid microstructures in the PS-P2VP film spin-cast from a TCE solution. After I2 staining, P2VP microdomains are dark and PS microdomains is bright. (b) UV–Vis spectra of the low-order gyroid PS-P2VP film in ethanol (dashed red line) and after complete evaporation of the ethanol (solid black line). 99
Figure 4-36. A series of cross-sectional TEM micrographs of the as-spun PS-P2VP/PS/P2VP ternary-blend films with various weight fractions of PS and P2VP homopolymers. (a) 10, (b) 20, (c) 30, (d) 40 and (e) 50 wt%. Solvent: TCE. 101
Figure 4-37. Ultraviolet–visible–near-infrared spectra of the TOSC-featured PS-P2VP/PS/P2VP ternary-blend films with various weight fractions of additive homopolymers from 10 to 50 wt%. Arrows are the reflections attributed to the (220) planes of the gyroid lattice. 104
Figure 4-38. Ultraviolet–visible–near-infrared spectra of the TOSC-featured PS-P2VP/PS/P2VP(50) ternary-blend films with various film thicknesses, including 3.2, 4.4, 5.5 and 7.2 μm. 107
Figure 4-39. Ultraviolet–visible–near-infrared spectra of BCP reflectors fabricated by stacking of PS-P2VP or/and PS-P2VP/PS/P2VP photonic crystal films after TOSC treatment. (a) A reflector with gradient reflection by stacking of PS-P2VP/PS/P2VP(10~50) ternary-blend films. (b) A complete full-visible-wavelength reflector fabricated by staking 3 layers of blue-colored films, 2 layers of green-colored films and 2 layers of red-colored films as illustrated. 108
Figure 4-40. (a) FESEM micrograph of the blue-colored wing scale of Ara ararauna (red circle). Cross-sectional TEM micrographs of PS-P2VP films spin-cast from various solvents. (b) 1,1,2 trichloroethane (TCE), (c) 1,2 dichloroethane (DCE), (d) chloroform and (e) dichloromethane (DCM). 111
Figure 4-41. SAXS profiles of the PS-P2VP films spin-cast from various solvents. 115
Figure 4-42. UV–Vis spectra of the TOSC-featured PS-P2VP films measured at different angles. (a) 1,1,2 trichloroethane (TCE), (b) 1,2 dichloroethane (DCE), (c) chloroform and (d) dichloromethane (DCM). 118
Figure 4-43. Tapping-mode SPM images of (a) as-spun film from chloroform and (b) followed with TOSC treatment. (c) WCA measurements of the as-spun film (86°) and TOSC-featured film (52°). 119
Figure 4-44. UV–Vis spectra of the TOSC-featured bicontinuous PS-P2VP films from chloroform with various thicknesses (0.6, 1.0, 1.7 and 2.1 µm). 120
Figure 4-45. UV–Vis spectra of the (a) one-layered and (b) 10-layered bicontinuous PS-P2VP APC films after TOSC treatment. 122
Figure 4-46. UV–Vis spectra of the 4-layered bicontinuous PS-P2VP APC films measured at various angles of light source after TOSC treatment. 123
Figure 4-47. Cross-sectional TEM micrographs and UV–Vis spectra of the TOSC-featured spongy-forming PS-P2VP trernary-blend films with various weight fractions of homopolymers. (a) (b) 10wt%, (c) (d) 20 wt% and (e)(f) 30wt%. 125
Figure 4-48. Short-range-order bicontinuous PS-P2VP APC films with wide-range reflectance wavelength from UVA(385nm) to NIR (766nm). 126

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