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(Title of the Thesis)* BLOCK COPOLYMER SELF-ASSEMBLY, HIERARCHICAL ASSEMBLY, AND APPLICATION by Xiaoyu Li A thesis submitted to the Graduate Program in Chemistry in conformity with the requirements for the Degree of Doctor of Philosophy Queen’s University Kingston, Ontario, Canada (January, 2013) Copyright ©Xiaoyu Li, 2013 Abstract This thesis addresses three issues. These are the self-assembly of block copolymer in selective solvents, hierarchical assembly of micelles or crosslinked micelles of block copolymers, and the application of block copolymers as solid state compatibilizers in polymer-based photovoltaic cells. Poly(acrylic acid)-block-(2-cinnamoyloxylethyl methacrylate)-block- poly(perfluorooctylethyl methacrylate) or PAA-b-PCEMA-b-PFOEMA self-assembles in solvent mixtures of α,α,α-trifluorotoluene (TFT) and methanol, which are selective towards PAA. At TFT volume fraction (fTFT) of 40 %, the copolymer forms vesicles at 70 oC and cylinders at 21 oC. These two structures inter-convert via meta-stable intermediates including jellyfish-like, tethered vesicular, and bilayer sheet-like structures. These structures occur in kinetic experiments involving quick temperature swing from 21 to 70 oC or vice versa and also in experiments involving annealing samples long at temperatures between 21 to 70 oC. Thus, they are meta-stable and point to complex pathways for the morphological transition. At fTFT = 10 %, the polymer forms vesicles with bumpy surface at 70 oC and toroids with sharp angles at 21 oC. Closely examined is how the liquid crystalline nature of the PFOEMA block affects the formation of these unique morphologies and their morphological transitions. Two types of hierarchical assembly of cylindrical micelles (cylinders) or crosslinked cylindrical micelles (fibers) of block copolymers are examined. First, carboxyl-bearing nanofibers of PAA-b-PCEMA and amino-bearing nanocylinders from poly(tert-butyl acrylate)-block-poly(2-cinnamoyloxyethyl methacrylate)-block-poly(2-dimethylamino- ii ethylmethacrylate), PtBA-b-PCEMA-b-PDMAEMA, are mixed in solvent. The two species firstly aggregate via electrostatic interaction. Upon heating and aging, the cylinders dissociate on the fibers and eventually evolve into composite multilayered cylindrical structures. Second, layer-by-layer (LBL) deposition of carboxyl- and amine- bearing nanofibers yielded multilayer films. These films detached from a substrate separate nanospheres based on their size and surface charge differences. Diblock copolymers poly(3-hexylthiophene)-block-poly(2-cinnamoyloxyethyl methacrylate-random-2-[6,6]-phenyl-C61-butyroyoxyethyl methacrylate) (T-C60C) and poly(3-hexylthiophene)-block-poly(2-acetoxyethyl methacrylate-random-2-[6,6]-phenyl- C61-butyroyoxyethyl methacrylate) (T-C60A) are synthesized and used as compatibilizers for polymer-based photovoltaic cells containing poly(3-hexylthiophene) and [6,6]- phenyl-C61-butyric acid methyl ester (PCBM). Both copolymers can stabilize the morphology of the active layer and thus the device performance. T-C60A in the active layer yields longer life-times and better initial performance of the devices, due to the matching of surface tensions between C60A and PCBM. iii Acknowledgements Firstly, I want to express my sincere appreciation to Dr. Guojun Liu, for his inspiration, guidance and patience in the last six years. Without his kindest help, I would not become what I am today. I sincerely hope that I have become a chemist as expected. Then I would like to express my gratefulness to all of the post-doctorate fellows who have contributed to my development over the years: Drs. Xiaohu Yan, Ronghua Zheng, Gabriel Njikang, Dehui Han, Liangzhi Hong, Dean Xiong and Hongbo Wang. I would also like to express my thanks to all the former and current Liu Group graduate students who have contributed with ideas and support: John Dupont, Nan Wang, Zhihan Zhou, Qiliang Peng, Yu Wang and Weijie Jiang. I also would like to express my appreciation for Jian Wang for measuring my AFM samples and Dr. Ian Wyman for proofreading this thesis. The work in this thesis was supported financially through NSERC and the Department of Chemistry at Queen's University. Lastly, I would like to thank my beloved Yang Gao. Without her help and care, my dream would not have come true. iv Statement of Originality I hereby certify that all of the work described within this thesis is the original work of the author. Any published (or unpublished) ideas and/or techniques from the work of others are fully acknowledged in accordance with the standard referencing practices. (Xiaoyu Li) (January, 2013) v Table of Contents Abstract ............................................................................................................................................ ii Acknowledgements ......................................................................................................................... iv Statement of Originality ................................................................................................................... v Table of Contents ............................................................................................................................ vi List of Figures ................................................................................................................................. ix List of Tables ................................................................................................................................. xii List of abbreviations ..................................................................................................................... xiii Chapter 1 Introduction and Literature Review ............................................................................... 1 1.1 Thesis Organization ................................................................................................................... 1 1.2 Block Copolymer Micelles in Selective Solvents ...................................................................... 5 1.2.1 Experimental and Theoretical Studies on Diblock Copolymer Micelles in Selective Solvents .................................................................................................................................... 6 1.2.2 Experimental Investigations on the Morphologies of ABC Triblock Copolymer Micelles in Selective Solvents ............................................................................................... 12 1.2.3 Morphological Studies on the Self-Assembly of Block Copolymers Containing Side- Chain Liquid Crystalline Blocks in Solution ......................................................................... 21 1.3 Multi-Tiered Assembly of Block Copolymers ......................................................................... 26 1.3.1 Multi-Tiered Assembly of Block Copolymer Nanostructures in Solution ................... 26 1.3.2 Layer-By-Layer Assembly Using Block Copolymer Micelles as Building Blocks ...... 31 1.4 Polymer-Based Bulk Heterojunction Solar Cells ..................................................................... 36 1.4.1 Basic Concepts of Polymer-Based Bulk Heterojunction Solar Cells and Recent Developments in This Field ................................................................................................... 36 1.4.2 Block Copolymers as Compatibilizers in Polymer-Based BHJ Solar Cells ................. 48 1.5 Research Objectives ................................................................................................................. 50 1.5.1 Self-Assembly of Triblock Copolymers Bearing A Liquid Crystalline Block ............. 50 1.5.2 Multi-Tiered Assembly of Block Copolymers .............................................................. 52 1.5.3 Application of Block Copolymers as Compatibilizers for PV cells .............................. 53 References ...................................................................................................................................... 55 Chapter 2 Morphological Transitions of an ABC Triblock Copolymer Containing a Liquid Crystalline Block ................................................................................................................... 61 2.1 Introduction .............................................................................................................................. 61 vi 2.2 Experimental Section ............................................................................................................... 64 2.3 Results and Discussion ............................................................................................................ 67 2.3.1 Polymer Characterization .............................................................................................. 67 2.3.2 Morphological Transitions ............................................................................................ 68 2.4 Conclusions .............................................................................................................................. 89 References ...................................................................................................................................... 90 Chapter 3 ABC Triblock Copolymer Toroids and Vesicles with Bumpy Walls .......................... 94 3.1 Introduction .............................................................................................................................. 94 3.2 Experimental Section ..............................................................................................................
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