Download or read book Block Copolymer Self assembly a Computational Approach Towards Novel Morphologies written by Karim Raafat Gadelrab and published by . This book was released on 2019 with total page 140 pages. Available in PDF, EPUB and Kindle. Book excerpt: Spontaneous self-assembly of materials is a phenomenon exhibited by different molecular systems. Among many, Block copolymers (BCPs) proved to be particularly interesting due to their ability to microphase separate into periodic domains. Nonetheless, the rising need for arbitrary, complex, 3D nanoscale morphology shows that what is commonly achievable is quite limited. Expanding the range of BCPs morphologies could be attained through the implementation of a host of strategies that could be used concurrently. Using directed self-assembly (DSA), a sphere forming BCP was assembled in a randomly displaced post template to study system resilience towards defect creation. Template shear-like distortion seemed to govern local defect generation. Defect clusters with symmetries compatible with that of the BCP showed enhanced stability. Using 44 and 32434 Archimedean tiling templates that are incompatible with BCP six-fold symmetry created low symmetry patterns with an emergent behavior dependent on pattern size and shape. A variation of DSA is studied using modulated substrates. Layer-by-layer deposition of cylinder forming BCPs was investigated. Self-consistent field theory (SCFT) and strong segregation theory SST were employed to provide the understanding and the conditions under which particular orientations of consecutive layers were produced. Furthermore, deep functionalized trenches were employed to create vertically standing high-[chi] BCP structures. Changing annealing conditions for a self-assembled lamellar structure evolved the assembled pattern to a tubular morphology that is non-native to diblock copolymers. A rather fundamental but challenging strategy to go beyond the standard motifs common to BCPs is to synthesize multiblock molecules with an expanded design space. Triblock copolymers produced bilayer perforated lamellar morphology. SCFT analysis showed a large window of stability of such structures in thin films. In addition, a model for bottlebrush BCPs (BBCPs) was constructed to investigate the characteristics of BBCPs self-assembly. Pre-stacked diblock sidechains showed improved microphase separation while providing domain spacing relevant to lithography applications. A rich phase diagram was constructed at different block concentrations. The ability to explore new strategies to discover potential equilibrium morphologies in BCPs is supported by strong numerical modeling and simulations efforts. Accelerating SCFT performance would greatly benefit BCP phase discovery. Preliminary work discussed the first attempt to Neural Network (NN) assisted SCFT. The use of NN was able to cut on the required calculations steps to reach equilibrium morphology, demonstrating accelerated calculation, and escaping trapped states, with no effect on final structure.
Download or read book Computational Study of Self assembly in Block Copolymer superparamagnetic Nanoparticle Composites Under External Magnetic Fields written by Vinay Raman and published by . This book was released on 2014 with total page 147 pages. Available in PDF, EPUB and Kindle. Book excerpt: This computational and theoretical study investigates the self-assembly of superparamagnetic nanoparticles and block copolymers under external magnetic fields. A variety of morphological transitions are observed based on the field orientation, nanoparticle loading, and selectivity of the nanoparticles for the blocks. For symmetric block copolymers, chaining of superparamagnetic nanoparticles under in-plane magnetic fields is shown to achieve long range orientational order of the block copolymer nanodomains and is found to be dependent on nanoparticle size, volume fraction and magnetization strength. A critical selectivity of the particles for one nanodomain is observed, above which strong alignment results and below which comparatively disordered structures are formed. Higher magnetization strengths are found to reduce equilibrium defect densities in the nematic-isotropic ordering of lamellar thin films, as corroborated by scaling arguments. For asymmetric coil fractions forming hexagonal block copolymer nanostructure, the inplane field induced chaining of the nanoparticles selective for the minority block, leads to the formation of stripe phases oriented parallel to the magnetic field. Furthermore, in-plane field induced chaining of nanoparticles selective for the majority block leads to alignment of hexagonal morphology with 100 direction oriented parallel to the external magnetic field. Out of plane magnetic fields induce repulsive dipolar interactions between the nanoparticles that annihilate the defects in the hexagonal morphology of the block copolymer when the nanoparticle is selective for the minority block. Honeycomb lattices are obtained using nanoparticles selective for majority block under out of plane magnetic fields for certain specific nanoparticle loadings. Commensurability of nanoparticle size and loadings with the block copolymer structure is critical in optimizing the ordering of the final composite. Kinetics of alignment in block copolymer nanocomposites is studied using External Potential Dynamics (EPD) method, wherein an equivalent evolution equation for potential fields is solved instead of conservation equation for the monomer segments. The dynamics study reveals an interesting interplay of nanoparticle mobility, dipolar interaction strength and nanoparticle-polymer interaction strength on the rate of alignment of domains.
Download or read book Amphiphilic Block Copolymers written by P. Alexandridis and published by Elsevier. This book was released on 2000-10-18 with total page 449 pages. Available in PDF, EPUB and Kindle. Book excerpt: It is the belief of the editors of this book that the recognition of block copolymers as being amphiphilic molecules and sharing common features with other well-studied amphiphiles will prove beneficial to both the surfactant and the polymer communities. An aim of this book is to bridge the two communities and cross-fertilise the different fields. To this end, leading researchers in the field of amphiphilic block copolymer self-assembly, some having a background in surfactant chemistry, and others with polymer physics roots, have agreed to join forces and contribute to this book.The book consists of four entities. The first part discusses theoretical considerations behind the block copolymer self-assembly in solution and in the melt. The second part provides case studies of self-assembly in different classes of block copolymers (e.g., polyethers, polyelectrolytes) and in different environments (e.g., in water, in non-aqueous solvents, or in the absence of solvents). The third part presents experimental tools, ranging from static (e.g., small angle neutron scattering) to dynamic (e.g., rheology), which can prove valuable in the characterization of block copolymer self-assemblies. The fourth part offers a sampling of current applications of block copolymers in, e.g., formulations, pharmaceutics, and separations, applications which are based on the unique self-assembly properties of block copolymers.
Download or read book Block Copolymers in Solution written by Ian W. Hamley and published by John Wiley & Sons. This book was released on 2005-12-13 with total page 300 pages. Available in PDF, EPUB and Kindle. Book excerpt: This unique text discusses the solution self-assembly of block copolymers and covers all aspects from basic physical chemistry to applications in soft nanotechnology. Recent advances have enabled the preparation of new materials with novel self-assembling structures, functionality and responsiveness and there have also been concomitant advances in theory and modelling. The present text covers the principles of self-assembly in both dilute and concentrated solution, for example micellization and mesophase formation, etc., in chapters 2 and 3 respectively. Chapter 4 covers polyelectrolyte block copolymers - these materials are attracting significant attention from researchers and a solid basis for understanding their physical chemistry is emerging, and this is discussed. The next chapter discusses adsorption of block copolymers from solution at liquid and solid interfaces. The concluding chapter presents a discussion of selected applications, focussing on several important new concepts. The book is aimed at researchers in polymer science as well as industrial scientists involved in the polymer and coatings industries. It will also be of interest to scientists working in soft matter self-assembly and self-organizing polymers.
Download or read book Synthesis Characterization and Self assembly of Amphiphilic Block Copolymers written by Xiaojun Wang and published by . This book was released on 2012 with total page 250 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation presents a review on state-of-the-art research of well-defined charged block copolymers, including synthesis, characterization, bulk morphology and self-assembly in aqueous solution of amphiphilic block polyelectrolytes. In Chapter 1, as a general introduction, experimental observations and theoretical calculations devoted towards understanding morphological behavior in charged block copolymer systems are reviewed along with some of the new emerging research directions. Further investigation of charged systems is urged in order to fully understand their morphological behavior and to directly target structures for the tremendous potential in technological applications. Following this background, in Chapters 2, 3, 4 and 5 are presented the design and synthesis of a series of well-defined block copolymers composed of charged and neutral block copolymers with full characterization: sulfonated polystyrene-b-fluorinated polyisoprene (sPS-b-fPI) and polystyrene-b-sulfonated poly(1,3-cyclohexadiene) (PS-b-sPCHD). Their bulk morphological behaviors in melts and self-assembly of sPS-b-fPI, PS-b-sPCHD in water were investigated. Some unique behaviors of sPS-b-fPI were discovered. The mechanisms for formation of novel nanostructures in aqueous solution are discussed in details in Chapter 4. Spherical and vesicular structures were formed from strong electrolyte block copolymers, e.g. PS-bsPCHD. Detailed light scattering and transmission electron microscopy were applied to characterize these structures. The abnormal formation of vesicles as well as microstructure effects on self-assembly is discussed in Chapter 5. In Chapter 6, we describe the successful synthesis of a well-defined acid-based block copolymers containing polyisoprene while maintaining the integrity of the functionality (double bonds) of polyisoprene. A general purification method is also presented in order to remove homo polyisoprene, polystyrene, and PS-b-PI in the di-, and tri-block copolymers. The self-assembly of PS-b-PI-b-PAA triblock terpolymers was studied in order to form multicompartmental structures in aqueous environments. In the last Chapter 7, detailed synthesis and characterization of a novel conjugate: poly(L-leucine) grafted hyaluronan (HA) (HA-g-PLeu) are presented. This work describes a new method to synthesize HA-g-PLeu via a "grafting onto" strategy. Due to the amphiphilic nature of this graft copolymers, a "local network" formed by self-assembly which was characterized by atomic force microscopy and light scattering. The secondary structure of the polypeptide was revealed by circular dichroism.
Download or read book Modeling and Theoretical Design Methods for Directed Self assembly of Thin Film Block Copolymer Systems written by Adam Floyd Hannon and published by . This book was released on 2014 with total page 324 pages. Available in PDF, EPUB and Kindle. Book excerpt: Block copolymers (BCPs) have become a highly studied material for lithographic applications due to their ability to self-assemble into complex periodic patterns with feature resolutions ranging from a few to 100s nm. BCPs form a wide variety of patterns due the combination of their enthalpic interactions promoting immiscibility between the blocks and the bonding constraint through their chain topology. The morphologies formed can be tailored through a directed self-assembly (DSA) process using chemical or topographical templates to achieve a desired thin film pattern. This method combines the traditional top-down lithographic methods with the bottom-up self-assembly process to obtain greater control over long range order, the local morphology, and overall throughput of the patterns produced. This work looks at key modeling challenges in optimizing BCP DSA to achieve precision morphology control, reproducibility, and defect control. Modeling techniques based on field theoretic simulations are used to both characterize and predict the morphological behavior of a variety of BCPs under a variety of processing conditions including solvent annealing and DSA under topographical boundary conditions. These methods aid experimental studies by saving time in performing experiments over wide parameter spaces as well as elucidating information that may not be available by current experimental techniques. Both forward simulation approaches are studied where parameters are varied over a wide range with phase diagrams of potential morphologies characterized and inverse design approaches where given target patterns are taken as simulation input and required conditions to produce those patterns are outputted from the simulation for experimental testing. The studies ultimately help identify the key control parameters in BCP DSA and enable a vast array of possible utility in the field.
Download or read book Block Copolymer Self assembly written by Gayashani Kanchana Ginige and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Molecular self-assembly is the basis of structure in nature. While of far less complexity than a natural system, the same physical rules apply to simple synthetic designed systems that spontaneously form self-assembled structures and patterns. The self-assembly of block copolymers (BCPs) is an interesting example, as it can be harnessed to form both 2D (in thin films) and 3D (in bulk) porous and chemically controlled morphologies at scale. The self-assembly of BCPs on surfaces is of interest for a range of applications, but due to the enormous economic driver that is the computer industry, this direction has been pushed most strongly. Self-assembly of BCPs has been described in the International Technology Roadmap for Semiconductors (the ITRS, and now the IDRS) for almost two decades for lithography on semiconductors and for patterning the magnetic material of hard drives. As a result, there has been much academic interest, both fundamental and applied, to meet the challenges as outlined in the ITRS/IDRS due to the promise of this scalable and low-cost nanopatterning approach. More recently, the remarkable work harnessing BCP self-assembly has been directed to other applications, one being optical metamaterials; this thesis will add to this growing body of science. One aspect holding BCP self-assembly back is the defectivity in the patterned material or surface; some applications are more defect tolerant than others, but hard drive and other computer-industry applications have very low tolerance for defects. It is, therefore, important to have systematic control over the self-assembly process as well as quality of the final patterns generated by BCP self-assembly for these applications and others not yet imagined. This thesis examines the defectivity of the hexagonal nanoscale patterns derived from BCP self-assembly and looks at extending them to produce nanoscale patterns of native and non-native morphologies that have plasmonic properties. This thesis is divided into two parts. The first part deals with optimization of solvent vapor annealing of BCP self-assembly, the critical step in which the actual nanoscale phase segregation takes place; in this case, it uses a controlled solvent vapor flow annealing apparatus, design of experiment and machine learning approaches. In this work, it was discovered that slight variations in the initial film thickness on the order of even a couple of nanometers and the final swelling degree have a huge influence on the defectivity and the quality of the resulting patterns. Next, machine learning approaches are applied to compile qualitative and quantitative defect analysis into a single figure of merit that is mapped across an experimental parameter space. This approach enables faster convergence of results to arrive at the optimum annealing conditions for the annealing of thin films of BCPs of PS-b-PDMS that generate nanoscale hexagonal patterns of silica dots with a minimum number of defects. In the second part of the thesis, mixed metal/oxide double layer patterning was studied using sequential self-assembly of BCPs. The second part of the thesis starts with optimization of reactive ion etching (RIE) for producing single layer metal nanopatterns from metal ion-loaded thin films of PS-b-P2VP BCPs to generate single layers of hexagonal metal nanopatterns that can withstand a second consecutive reactive ion etching step. The goal of this work is to enable density doubled and/or Moiré pattern formation via self-assembly of a second layer of BCP on the initial pattern prepared by self assembly of either the same or different BCP, as will be described in Chapter 4. Therefore, the initial pattern produced via BCP self-assembly and RIE etching would need to withstand a second treatment step of BCP self-assembly and RIE. While single layer nanopatterns of Au and Pt nanoparticles can be produced without much trouble, these resulting patterns could not be applied for density multiplication of metal-metal nanopatterns since the metal dots become too small and disordered. To demonstrate that metal nanoparticles derived from BCPs could be used, at least, to produce a mixed metal oxide/metal patterns, arrays of SiOx dots were first produced from PS-b-PDMS BCPs and then layered a BCP of PS-b-P2VP that was subsequently loaded with gold or platinum ions. Upon RIE etching, the BCP is removed and the SiOx/Au or Pt nanoparticle arrays were produced. Based upon the outcomes of the optimization of the etching work, mixed Au-Pt commensurate and incommensurate hexagonal lattice patterns were produced on both silicon and quartz substrates. Finally, the optical properties of these mixed metal Pt-Au bilayer patterns were studied. They demonstrated interesting plasmonic properties of the bilayer patterns, including consistent observation of extended plasmon bands that suggest coupling of the localized surface plasmon resonances (LSPRs) of the gold nanoparticles through proximal platinum nanoparticles when arrayed in periodic patterns.
Download or read book Block Copolymer Self assembly and Application for Polymer Electrodes written by Sirikorn Chasvised and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis is part of the global effort to find alternative energies to those generating CO2, a greenhouse gas. Indeed, electrodes are herein developed to produce hydrogen from the electrolysis of water. Specifically, block copolymers were developed for use as a binder in ink formulations for electrode screen printing. After presenting a state of the art in the first chapter, we decided to study the effect of microwaves on the self-assembly and the hierarchical structuration of our first polymer binder, a block copolymer (MBM) based on methyl methacrylate (MMA) and butyl acrylate (BuA). The polymer films were annealed under microwave irradiation of 60 seconds at 10 watts. Atomic force microscopy (AFM) was used to study the orientation of the nano-segregation without destruction of the microstructure. Then this MBM copolymer was used as a binder to produce polymer electrodes by screen printing. The MBM is mixed with conductive graphite particles and then printed on the NAFION substrate to produce an electrode. These electrodes were functionalized with a ruthenium catalyst supplied by the group of Prof. Antoni Llobet and were used in the water oxidation process. We then worked on the synthesis and film structuration of a second block copolymer based on poly (3-hexylthiophene) (P3HT). The conjugated copolymer P3HT-b-PMMA was synthesized by coupling reaction via "click" chemistry. We demonstrate changes in the self-assembly morphology of the copolymer, by introducing an ionic group at the binding unit between the two blocks. Second, we use microwave annealing to destroy the P3HT fibrils. We observe that after annealing at 30W for 1 minute the fibrils disappear and highly ordered morphologies are successfully created. Finally, we present the synthesis of a new macromolecular catalyst based on P3HT to be integrated into the electrode for the production of hydrogen (reduction of protons). A simple, copper-free cycloaddition process is presented to couple a complex cobalt catalyst (provided by Vincent Artero's group) and the polymer. The electrochemical properties of the P3HT-Co catalyst were characterized by cyclic voltammetry.
Download or read book Solvent Vapor Assisted Self Assembly of Patternable Block Copolymers written by Joan K. Bosworth and published by . This book was released on 2009 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Block copolymer self assembly presents a method for patterning and templating applications on the 10-50 nm length scale, a smaller scale than can be easily achieved by photolithography. Here we investigate the use of functionalized polar-nonpolar block copolymers both as photopatternable self-assembling materials and for selective infiltration of one block for patterning. Block copolymer thin films with defect-free self-assembled morphology over large domains combined with careful control of the orientation of the morphology are critical for these patterning applications. Self assembly of block copolymers is facilitated by polymer chain mobility, commonly achieved by heating block copolymer films above the glass transition temperature of the blocks. However, many block copolymer systems, including those discussed here, are thermally incompatible. Swelling in a solvent vapor, called solvent annealing, provides sufficient mobility for self assembly. Solvent annealing proved critical to forming ordered structures of functional polar-nonpolar block copolymer thin films. Thermal instability initially led to limited self assembly of combined topdown/bottom-up block copolymer systems. In this case, photolithographic functionality has been designed into block copolymers, allowing the majority component of a block copolymer to behave as a negative-tone photoresist. Solvent vapor annealing has provided a simple and inexpensive method for allowing the bottom-up self assembly of these top-down photopatternable materials. An additional benefit of solvent annealing is the ability to reversibly tune the morphology formed using the selectivity of different swelling solvents to the two blocks: that is, the choice of solvent for annealing directs the formation of different morphologies in the dried film, here spherical and cylindrical. This behavior is reversible, alternating annealing sessions lead to switching of the morphology in the film. Secondary ordering techniques applied in tandem with solvent annealing can be used to further control the self assembly and give highly ordered block copolymer domains. Here we demonstrate the use of graphoepitaxy to align block copolymer self assembly to patterns in substrates. The combination of block copolymer self assembly with lithographic crosslinking in films was initially pursued to allow precise location of assembled patterns. Taking this behavior a step further, we combine solvent annealing, used to reversibly tune the self-assembled morphology, and lithographic patterning, used to prevent switching in exposed regions. This combined process has provided a method for selectively patterning 100 nm-wide domains of spherical morphology within regions of parallel-oriented cylindrical morphology. We also investigate solvent annealing of a block copolymer blended with a hydrogen bonding material that selectively segregates into the polar block. Blending provides a method of tuning the periodicity upon solvent annealing for self assembly, with morphology control again possible by solvent selectivity. Selective extraction of the blended material forms voids displaying the tunable periodicity, and the pattern is then transferred by templating to inorganic materials.
Download or read book Investigating the Role of Topological Frustration on Morphology of Novel Multiblock Copolymers written by Rohit Gupta and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Multiblock copolymers have gained considerable attention due to their ability to offer immense potential for designing soft materials with complex architectures for diverse applications. The enlarged parameter space offered by these multiblock copolymers gives access to a wide variety of multiply continuous morphologies which can be used to produce highly ordered nanostructures. The investigation on multiblock copolymers has been subjected to two critical limitations: (i) A suitable synthetic strategy for accessing these structures and (ii) computational tools which can help in application driven design of these molecules. In this dissertation, the goal was to develop methodologies for the synthesis of multiblock copolymers with different architectures and understand how the variations in molecular architecture can influence macromolecular self-assembly. In chapter 2, the concept of single molecule insertion (SMI) for precise insertion of functional molecules is presented. The molecule precisely inserts once within the polymer chain with high chain fidelity and provides functionalities for post-insertion modifications. A series of molecules satisfying the criteria for SMI based on their reactivity ratios with styrene and methyl methacrylate were examined and used to synthesize a series of multiblock polymers with complex architectures. In chapter 3, a highly efficient synthetic methodology for synthesis of graft copolymers which lie along the continuum of a 3-arm star and A-B-C linear triblock copolymer has been described. The morphological characterization of the synthesized continuum graft copolymers is performed using SAXS, TEM, and DPD simulations. Interesting morphologies are observed for these continuum copolymers and projects them as interesting candidates to access new morphologies. Contrary to most of the work done on block copolymers, these structures are novel as their morphologies can be tuned keeping the [phi] and [chi] constant. This study helps in understanding of the effect of polymer architecture on the phase behavior of these graft copolymers and provides a novel pathway to tune the block copolymer morphologies. In chapter 4, a series of PMMA-b-PtBS-b-P2VP and PtBA-b-PtBS-b-P2VP triblock copolymers with extending P2VP arm has been synthesized. The study helps in extending the concept of high [chi]-low N block copolymer system from diblock to triblock copolymers. The morphologies of the synthesized triblock copolymers were characterized using SAXS and TEM and morphologies with multiple domains and smaller feature size were observed. Also, the effect of extending chain length of P2VP arm on the phase diagram on these highly frustrated triblock copolymer systems was studied and the observed morphologies using SAXS and TEM were mapped with the theoretical predictions.
Download or read book Computational Design and Morphology Engineering of Multiblock Polymer Films written by Sean Phillip Paradiso and published by . This book was released on 2015 with total page 132 pages. Available in PDF, EPUB and Kindle. Book excerpt: The primary drive of our investigation is to understand pattern selection during solvent evaporation, a method for producing block copolymer materials that is gaining popularity due to the control it offers over the self assembly process. To this end, we describe a field-based dynamics method for simulating the microphase separation process during solvent evaporation and offer insights into the physical parameters that appear to govern the process.
Download or read book Part I Morphology Transformation of Block Copolymer Micelles Containing Quantum Dots in the Corona written by Meng Zhang and published by . This book was released on 2013 with total page 378 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Selective Directed Self assembly of Coexisting Morphologies Using Block Copolymer Blends written by and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Directed self-assembly (DSA) of block copolymers is an emergent technique for nano-lithography, but is limited in the range of structures possible in a single fabrication step. We expand on traditional DSA chemical patterning. Moreover, a blend of lamellar- and cylinder-forming block copolymers assembles on specially designed surface chemical line gratings, leading to the simultaneous formation of coexisting ordered morphologies in separate areas of the substrate. The competing energetics of polymer chain distortions and chemical mismatch with the substrate grating bias the system towards either line/space or dot array patterns, depending on the pitch and linewidth of the prepattern. This contrasts with typical DSA, wherein assembly of a single-component block copolymer on chemical templates generates patterns of either lines/spaces (lamellar) or hexagonal dot arrays (cylinders). In our approach, the chemical template encodes desired local spatial arrangements of coexisting design motifs, self-assembled from a single, sophisticated resist.
Download or read book Block Copolymer Self assembly and Templating Strategies written by Wubin Bai and published by . This book was released on 2016 with total page 136 pages. Available in PDF, EPUB and Kindle. Book excerpt: Block copolymers microphase separate to form periodic patterns with period of a few nm and above without the need for lithographic guidance. These self-assembled nanostructures have a variety of bulk geometries (alternating lamellae, gyroids, cylinder or sphere arrays, tiling patterns, core-shell structures) depending on the molecular architecture of the polymer and the volume fraction of its blocks. And in thin films, surface interaction and commensurability effect influence the self-assembly and result in more diverse morphologies including hexagonal-packed perforated lamellae, square array of holes. The progress of self-assembly can be tracked in situ using Grazing Incidence Small Angle X-ray Scattering, and the annealed morphology can be revealed in 3D using TEM tomography. Moreover, non-bulk morphologies can be produced, the ordering of the microdomains can be improved and their locations directed using various templates and processing strategies. The blocks can themselves constitute a functional material, such as a photonic crystal, or they can be used as a mask to pattern other functional materials, functionalized directly by various chemical approaches, or used as a scaffold to assemble nanoparticles or other nanostructures. Block copolymers therefore offer tremendous flexibility in creating nanostructured materials with a range of applications in microelectronics, photovoltaics, filtration membranes and other devices.
Download or read book Self assembly of Block Copolymers Grafted Onto a Flat Substrate Recent Progress in Theory and Simulations Project Supported by the National Natural Science Foundation of China Grant Nos 20990234 20925414 and 91227121 the Program for Changjiang Scholars and Innovative Research Team in University China Grant No IRT1257 the Programme of Introducing Talents of Discipline to Universities China and by the Tianhe No 1 China written by and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Abstract: Block copolymers are a class of soft matter that self-assemble to form ordered morphologies on the scale of nanometers, making them ideal materials for various applications. These applications directly depend on the shape and size of the self-assembled morphologies, and hence, a high degree of control over the self-assembly is desired. Grafting block copolymer chains onto a substrate to form copolymer brushes is a versatile method to fabricate functional surfaces. Such surfaces demonstrate a response to their environment, i.e., they change their surface topography in response to different external conditions. Furthermore, such surfaces may possess nanoscale patterns, which are important for some applications; however, such patterns may not form with spun-cast films under the same condition. In this review, we summarize the recent progress of the self-assembly of block copolymers grafted onto a flat substrate. We mainly concentrate on the self-assembled morphologies of end-grafted AB diblock copolymers, junction point-grafted AB diblock copolymers (i.e., Y-shaped brushes), and end-grafted ABA triblock copolymers. Special emphasis is placed on theoretical and simulation progress.
Download or read book Self assembly of Block Copolymers and Polymer Brushes written by Wei Wei and published by . This book was released on 2019 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Self-assembly of block copolymer materials (BCPs) and polymer brushes in the sub-50 nm length scale are explored in this thesis. BCPs and mixed polymer brushes have the ability to self-assemble into well-ordered structures which are ideal for surface patterning, templating and growth of nanomaterials. Compared to the extensively studied morphologies resulting from BCPs, phase behavior of mixed brushes is experimentally less explored, mainly due to the synthetic and characterization challenges. In this thesis we derive from the studies in the BCP self-assembly in thin films to study the melt phase behavior of mixed brushes on a planar substrate. In the first part of the thesis we study the thin film assembly of a strongly phase-separating cylinder forming poly(styrene-b-2 vinylpyridine) (PS-b-P2VP). The cylinders are used to template arrays of sub-20-nm-wide molybdenum disulfide (MoS2) nanowires. In the second part of the thesis we develop a synthetic route to grow uniform, high-grafting density polymer brushes with controlled brush length on planar substrates. This method starting from an initiator coating overcomes all the previous synthetic challenges. This chemistry is first tested by growing a mixed brush poly(methyl methacrylate)/polystyrene (PMMA/PS). We validate for the first time the predicted morphology for mixed brush in melt using the PS/PMMA. The deviation from the expected phase behavior as we move to strongly segregating PS/P2VP mixed brush system is discussed. Lessons learned from the thin film assembly of the PS-b-P2VP in the first part of the thesis led to the largely unexplored area of chain-end effects on morphology in mixed polymer brushes. Potential solutions towards the self-assembly of PS/P2VP mixed bushes in melt is discussed. Three major contributions are made in this thesis: 1) development of an universal method to synthesize A/B mixed brushes with uniform grafting of A/B chains; 2) development of a model to experimentally evaluate the grafting densities of the two brushes; and 3) discovery of chain end effect on thermal stability of mixed brushes and its influence on the morphology. This thesis paves the way for synthesizing mixed brushes with unprecedented level of control, hence opening up new phase behavior and potential surface patterning methods.
Download or read book Synthesis and Self assembly of Advanced Bottlebrush Block Copolymers written by Justin Bolton and published by . This book was released on 2012 with total page 150 pages. Available in PDF, EPUB and Kindle. Book excerpt: Using the grafting-from approach, three novel well-defined bottlebrush block copolymers were synthesized using various controlled polymerization techniques. Resulting macromolecules were characterized by GPC and 1H NMR and then self-assembled into nanostructured materials for further characterization. Asymmetric polystyrene-polylactide (PS-PLA) bottlebrush block copolymers have been shown to self-assemble into a cylindrical morphology with large domain spacings. PLA cylinders can be selectively etched out of the shear-aligned polymer monoliths to generate nanoporous materials with an average cylindrical pore diameter of 55 nm. The remaining bottlebrush backbone provides a functional, hydrophilic coating inside the nanopores. This methodology significantly expands the range of pore sizes attainable in block copolymer based nanoporous materials.^A polystyrene-poly(methyl methacrylate) (PS-PMMA) bottlebrush block copolymer with asymmetric branches was synthesized by grafting from a symmetrical backbone containing a novel dual vinyl initiation system and characterized by atomic force microscopy (AFM) and small-angle x-ray scattering (SAXS). The block copolymer backbone was prepared by sequential reversible addition-fragmentation chain transfer (RAFT) copolymerization of solketal methacrylate and 2-(bromoisobutyryl)ethyl methacrylate (BIEM). From the poly(BIEM) segment, PMMA branches were grafted by atom transfer radical polymerization (ATRP). Solketal groups were then subjected to hydrolysis and functionalized with a RAFT agent. Subsequently, from RAFT sites of the poly(SM) segment, polystyrene branches were grafted to yield the final bottlebrush block copolymer.^The resulting polymer was found to have a vertically oriented cylindrical morphology by AFM with an average cylinder diameter of 45 nm; morphology was also confirmed by SAXS analysis. A novel polylactide-poly(methyl methacrylate)-polystyrene (PLA-PMMA-PS) triblock bottlebrush block copolymer was synthesized from a triblock backbone employing ATRP, RAFT and ROP techniques. Novel 5-TMS-4-pentyn-1-ol methacrylate (TPYM) with protected alkyne functionality was developed and characterized as a homopolymer. Click chemistry was used to introduce RAFT groups along the homopolymer backbone. Subsequently, PS branches were grafted from RAFT initiators along the backbone. A well-defined poly(SM-b-BIEM-b-TPYM) backbone was synthesized followed by grafting of PMMA brushes from the BIEM segment by ATRP.^Post PMMA grafting, the ATRP end groups were removed and the TMS group was deprotected to allow functionalization of the alkyne with an azido terminated RAFT agent by way of Huisgen 1,3-dipolar cycloaddition. From the RAFT sites, PS was grafted followed by deprotection of the hydroxyl functionality of the SM block. Resulting liberated hydroxyls were used to initiate PLA grafts, yielding the final well-defined triblock bottlebrush block copolymer (PLA-PMMA-PS).