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研究生： 倪伊娃
Oktavia, Eva
論文名稱： 塊狀聚合物薄膜在中性溶劑下的結構研究
Study on Morphological Development of Diblock Copolymer Thin Film under Neutral Solvent Annealing
指導教授： 羅介聰
Lo, Chieh-Tsung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2009
畢業學年度： 97
語文別： 英文
論文頁數： 82
中文關鍵詞： 非均相成核 、去溼 、薄膜 、回火
外文關鍵詞： diblock copolymer, annealing, heterogeneous nucleation, spinodal dewetting, dewetting, thin film
相關次數： 點閱：72  下載：2 
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    • 摘要

    雙區間共聚合薄膜應用在奈米科技重要性已經被廣泛用於研究製備大範圍微結構陣列。 在此研究中我們著重於了解PS-PVP薄膜在中性溶劑回火的對稱型態發展。原子力顯微鏡被應用來調查回火時間.溶劑量.溶劑性質對PS-PVP薄膜的奈米結構的關聯。在不同中性溶劑中薄膜型態的發展已經有好的定性描述，但是在不同溶劑蒸氣壓造成的結構改變速率是不同的。對於低蒸氣壓的溶劑需要較長的時間和更多的溶劑量才能得到整齊的結構。

    得到最少缺陷長範圍區間的共聚合薄膜的過程中”去溼”是另一個必須要解決的基本問題。去溼機制已經在光學顯微鏡被證實，去溼機制和膨潤係數(Q)是相關聯的，而所謂的膨潤係數表示薄膜在溶劑蒸氣下膨潤行為的一個定量係數。在低的膨潤係數下，去溼行為是經由非均相成核發展而來。在高膨潤係數下靜止去溼行為支配整個去溼機制。不管中性溶劑的性質為何澎潤係數和去溼機制是有一致關係。

    關鍵詞 : 薄膜; 回火; 去溼; 非均相成核

    ABSTRACT

    The importance of diblock copolymer thin film on the application in nanotechnology has promoted extensive studies in obtaining long-range alignment of microstructures. In this study, we focus on the understanding of morphological evolution of symmetric polystyrene-b-poly(2-vinyl pyridine) (PS-PVP) thin film annealed in a neutral solvent. Atomic force microscopy (AFM) was employed to investigate the nanostructure of PS-PVP thin film as a function of the nature of the solvent, the quantity of the solvent, and annealing time. It was obtained that the development of morphology of thin film under different kinds of neutral solvents qualitatively agrees well, but the rate of structure change is different due to the different vapor pressure of these solvents. The solvent with lower vapor pressure takes longer time and more quantity of solvent to reach an ordered structure.

    Dewetting is another fundamental problem that has to be resolved in obtaining long range order of block copolymer thin film with the least defect. The dewetting mechanism was verified by optical microscopy, and the dewetting mechanism is correlated to the swelling coefficient (Q), which represents the quantity of the solvent that swells the thin film under solvent vapor treatment. At low Q, dewetting evolves via heterogeneous nucleation. At high Q, spinodal dewetting dominates the dewetting mechanism. The behavior of Q with respect to the dewetting mechanism is consistent regardless of the nature of neutral solvents.

    Keywords : thin film; annealing; diblock copolymer; dewetting; heterogeneous nucleation; spinodal dewetting

    TABLE OF CONTENTS ABSTRACT IN ENGLISH i ABSTRACT IN CHINESE ii ACKNOWLEDMENT iii LIST OF TABLE vii LIST OF FIGURES viii CHAPTER 1 INTRODUCTION 1 References 3 CHAPTER 2 LITERATURE REVIEW 4 2.1. Block Copolymer 4 2.2. Phase Behavior of Block Copolymer 4 2.3. Physical Properties of Block Copolymer 8 2.3.1. Miscibility 8 2.3.2. Surface Energy 9 2.4. Scaling Behavior of the Microdomains of Block Copolymer 10 2.4.1. Disordered State 11 2.4.2. Ordered State 12 2.5. Control Long Range Orientation of Microdomain Patterns 13 2.5.1. Control of Film Thickness 14 2.5.2. Control of Substrate-Polymer Interactions 16 2.5.3. Application of an External Field 18 2.6. Dewetting Behavior 18 2.6.1 Morphology of the Dewetting 20 2.7. References 23 CHAPTER 3 RESEARCH OBJECTIVES 28 3.1. Scope of Research 28 3.2. Overview of the Thesis 29 CHAPTER 4 EFFECT OF SOLVENT ANNEALING ON THE MORPHOLOGY OF POLYSTYRENE-b-POLY(2-VINYL PYRIDINE) THIN FILM 30 4.1. Abstract 30 4.2. Introduction 30 4.3. Experimental part 33 4.3.1. Materials 33 4.3.2. Substrate 34 4.3.3. Preparation of PS-PVP Thin Films 34 4.3.4. Characterization of PS-PVP Thin Films 34 4.4. Results and Discussion 35 4.4.1. The Swelling Coefficient 35 4.4.2. Microphase Separation of PS-PVP Thin Film 36 4.4.3. Dewetting of PS-PVP Thin Film 38 4.4.4. The Relationship between the Swelling Coefficient and Morphology of Thin Film 41 4.5. Conclusion 42 4.6. Acknowledgment 43 4.7. References 43 CHAPTER 5 MORPHOLOGICAL DEVELOPMENT OF SYMMETRIC POLYSTYRENE-b-POLY(2-VINYL PYRIDINE) DIBLOCK COPOLYMER THIN FILM UNDER NEUTRAL SOLVENT ANNEALING 54 5.1. Abstract 54 5.2. Introduction 54 5.3. Experimental Part 57 5.3.1. Materials 57 5.3.2. Substrate 57 5.3.3. Preparation of PS-PVP Thin Film 58 5.3.4. Morphology of PS-PVP Thin Film 58 5.3.5. Dewetting of PS-PVP Thin Film 58 5.4. Results and Discussion 58 5.4.1. The Development of Morphology of PS-PVP Thin Film under Chloroform Vapor 59 5.4.2. The Development of Morphology of PS-PVP Thin Film under Benzene Vapor 61 5.4.3. The Development of Morphology of PS-PVP Thin Film under Dichloromethane Vapor 62 5.4.4. Effect of the Amount of Solvent on the Morphology of PS-PVP Thin Film 63 5.4.5. Effect of Thin Film Morphology as a Function of the Swelling Coefficient 65 5.4.6. Effect of Swelling Coefficient on the Dewetting of PS-PVP Thin Film 66 5.5. Conclusion 68 5.6. Acknowledgment 69 5.7. References 69 CHAPTER 6 CONCLUSIONS 80 6.1. Summary 80

    CHAPTER 1 INTRODUCTION
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    12. Elbs H, Drummer C, Abetz V, Krausch G. Thin Film Morphologies of ABC Triblock Copolymers Prepared from Solution. Macromolecules 2002:35(14):5570-5577.
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    CHAPTER 2 LITERATURE REVIEW
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    CHAPTER 4 EFFECT OF SOLVENT ANNEALING ON THE MORPHOLOGY OF POLYSTYRENE-b-POLY(2-VINYL PYRIDINE) THIN FILM
    1. Li X, Peng J, Wen Y, Kim DH, Knoll W. Morphology Change of Asymmetric Diblock Copolymer Micellar Films during Solvent Annealing Polymer 2007: 48:2434-2244.
    2. Hashimoto T, Shibayama M, Fujimura M, Kawai H. In: Meier DJ, editor. Block Copolymers, Science and Technology. London: Harwood Academic, 1983.
    3. Hamley IW. The Physics of Block Copolymers. New York: Oxford University Press, 1998.
    4. Fasolka M, Mayes A. Annu Rev Mater Res 2001:323-355.
    5. Lin Z, Kim DH, Wu X, Boosahda L, Stone D, LaRose L, Russell TP. A Rapid Route to Arrays of Nanostructures in Thin Films. Adv Mater 2002:14(19):1373-1376.
    6. Buck E, Fuhrmann J. Surface-Induced Microphase Separation in Spin-Cast Ultrathin Diblock Copolymer Films on Silicon Substrate before and after Annealing. Macromolecules 2001:34:2172.
    7. Fukunaga K, Elbs H, Magerle R, Krausch G. Large-Scale Alignment of ABC Block Copolymer Microdomains via Solvent Vapor Treatment. Macromolecules 2000:33:947.
    8. Kim G, Libera M. Morphological Development in Solvent-Cast Polystyrene−Polybutadiene−Polystyrene (SBS) Triblock Copolymer Thin Films. Macromolecules 1998:31(8):2569-2577.
    9. Hanley KJ, Lodge TP, Huang CI. Phase Behavior of a Block Copolymer in Solvents of Varying Selectivity. Macromolecules 2000:33(16):5918.
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    CHAPTER 5 MORPHOLOGICAL DEVELOPMENT OF SYMMETRIC POLYSTYRENE-b-POLY(2-VINYL PYRIDINE) DIBLOCK COPOLYMER THIN FILM UNDER NEUTRAL SOLVENT ANNEALING

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    15. Peng J, Xuan Y, Wang HF, Li BY, Han YC. Solvent Vapor Induced Dewetting in Diblock Copolymer Thin Films. Polymer 2005:46(15):5767-5772.
    16. Peng J, Kim DH, Knoll W, Xuan Y, Li BY, Han YC. Morphologies in Solvent-Annealed Thin Films of Symmetric Diblock Copolymer. J Chem Phys 2006:125(6):064702.
    17. Xu T, Stevens J, Villa JA, Goldbach JT, Guarini KW, Black CT, Hawker CJ, Russell TP. Block Copolymer Surface Reconstuction: A Reversible Route to Nanoporous Films. Adv Funct Mater 2003:13(9):698-702.
    18. Xuan Y, Peng J, Cui L, Wang H, Li B, Han Y. Morphology Development of Ultrathin Symmetric Diblock Copolymer Film via Solvent Vapor Treatment. Macromolecules 2004:37(19):7301-7307.
    19. Ham S, Shin C, Kim E, Ryu DY, Jeong U, Russell TP, Hawker CJ. Microdomain Orientation of PS-b-PMMA by Controlled Interfacial Interactions. Macromolecules 2008: 41(17): 6431-6437.
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    25. Zope M, Kargupta K, Sharma A. Self-Organized Structures in Thin Liquid Films on Chemically Heterogeneous Substrates: Effect of Antagonistic Short and Long Range Interactions. The Journal of Chemical Physics 2001:114:7211.
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    27. Xie R, Karim A, Douglas J, Han C, Weiss R. Spinodal Dewetting of Thin Polymer Films. Physical Review Letters 1998:81(6):1251-1254.
    28. Reiter G. Unstable Thin Polymer Films: Rupture and Dewetting Processes. Langmuir 1993:9(5):1344-1351.

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