Title Page
ABSTRACT
국문 초록
Contents
CHAPTER 1. Introduction 17
1.1. Introduction 17
1.2. Block Copolymer Self-Assembly 20
1.3. Block Copolymer Self-Assembly in Thin Film 24
1.4. Bottlebrush Block Copolymer Self-Assembly 27
1.5. Directed Self-Assembly (DSA) 30
CHAPTER 2. Experimental Section 35
2.1. Materials 35
2.2. Synthesis Method 36
2.3. Synthesis of Bottlebrush Block Copolymers 39
2.3.1. Synthesis of NB-NRC 39
2.3.2. Synthesis of Macromonomer 42
2.3.3. Synthesis of Bottlebrush Homopolymer 47
2.3.4. Synthesis of Bottlebrush Block Copolymer 49
2.4. Preparetion of BBCP Thin Films & Characterization 53
2.5. Directed Self-Assembly of BBCPs 58
2.5.1. Shear-Rolling Process 58
2.5.2. Graphoepitaxy 61
CHAPTER 3. Results and Discussion 63
3.1. BBCP Thin Film Experimental Results 63
3.2. BBCP DSA Thin Film Experimental Results 65
3.2.1. Shear-Rolling Process Results 65
3.2.2. Graphoepitaxy Results 67
3.3. Conculsion & Summary 69
REFERENCES 70
Table 2.1. Characteristics of BBCP, (PNB-g-PS)-b-(PNB-g-PMA) 38
Figure 1.1. (a) Schematic phase diagram of BCP, (b) Various nanostructures formed by the self-assembly of BCPs 19
Figure 1.2. One-dimensional composition profile of two regimes (weak segregation limit, strong segregation limit) that have sinusoidal signals. 23
Figure 1.3. Schematic illustration of the substrate neutralization with various cross-linkable random copolymers. 26
Figure 1.4. (a) Bottlebrush block copolymer (b) (P(aPP)-b-P(PS)) SAXS profiles 29
Figure 1.5. Schematic of DSA by (a) chemoepitaxy and (b) graphoepitaxy 32
Figure 1.6. Schematic of DSA by graphoepitaxy in various orientations. (a) The side walls are selective to PMMA and the substrate is neutral for both blocks. (b) The side walls... 33
Figure 1.7. (a) Schematic illustration of the shear-rolling process. (b) Procedure of the shear-rolling process of filtered plasma-treated BCP thin films fabricating aligned nano-patterns. 34
Figure 2.1. Chemical structures and ¹H NMR spectrum of NB-COOH, NB-NRC in CDCl₃ 41
Figure 2.2. Gel Permeation Chromatography (GPC) results of (a) PS synthesized via ATRP, (b) PMA synthesized via ATRP, (c) norbornene group functionalized with PS,... 45
Figure 2.3. Chemical structures and ¹H NMR spectrum of (a) NB-PMA, and (b) NB-PS in CDCl₃ 46
Figure 2.4. Multi-Angle Light Scattering Detection (MALS) results of (a) PNB-g-PS, (b) PNB-g-PMA 48
Figure 2.5. Multi-Angle Light Scattering Detection (MALS) results of (a) PNB-g-PS bottlebrush homopolymer before sequential ROMP, (b) (PNB-g-PMA)-b-(PNB-g-PS)... 50
Figure 2.6. Differential Scanning Calorimetry (DSC) traces of (PNB-g-PMA)-b-(PNB-g-PS) with Mn=206kg/mol. The total heating rate was 10℃/min, and the cooling heating...[이미지참조] 51
Figure 2.7. SAXS intensity profiles of (PNB-g-PMA)-b-(PNB-g-PS) with Mn=206kg/mol after thermal annealing at 150℃. The number indexes are indicating the positions...[이미지참조] 52
Figure 2.8. Top view AFM images of lamellar-forming (PNB-g-PMA)-b-(PNB-g-PS) thin films (a) PNB₁₁₄(S₄k-b-MA₄k), (b) PNB₁₀₃(S₂k-b-MA₂k). Films were thermally...[이미지참조] 56
Figure 2.9. FE-SEM images of lamellar-forming (PNB-g-PMA)-b-(PNB-g-PS) thin films (a) PNB₁₁₄(S₄k-b-MA₄k), (b) PNB₁₀₃(S₂k-b-MA₂k) after thermally annealed at 150℃...[이미지참조] 57
Figure 2.10. Multi-Angle Light Scattering Detection (MALS) results of TEMPO based bottlebrush polymer after annealing at air condition for (a) 30 seconds, (b) 60 seconds,... 59
Figure 2.11. FE-SEM images of (a) thermally pre-annealed BBCP thin film for 150℃, 1 hour after filtered plasma treatment, (b) after 60 seconds shear-rolling process. 60
Figure 2.12. FE-SEM images of (a) side walls and substrate selective to PS, (b) side walls and substrate selective to PMA, and (c) side walls and substrate are neutral for both... 62
Figure 3.1. AFM and GI-SAXS images of lamellar-forming (PNB-g-PMA)-b-(PNB-g-PS) thin films (a) PNB₁₁₄(S₄k-b-MA₄k), (b) PNB₁₀₃(S₂k-b-MA₂k) after thermally annealed...[이미지참조] 64
Figure 3.2. FE-SEM images of the shear-rolling process at 90℃ for (a) 60 seconds and (b) 5 minutes. 66
Figure 3.3. FE-SEM images of graphoepitaxy results. Periodicity and width of trench was 300nm, 80nm in case of (a), (b), (c) and periodicity and width of trench was 1000nm,... 68
Scheme 2.1. Synthetic scheme of (PNB-g-PS)-b-(PNB-g-PMA) 37