If you have not read the section on chain extension in the procedures for initiation of. Block copolymer selfassembly in thin films can spontaneously generate periodic nanoscale patterns such as hexagonal arrays of dots or. Advances in this area could affect the manufacture of everything from computer chips to solar cells. Ablock bblock bcpblock copolymer living anionic polymerizing method. The selfassembly of block copolymers is mainly controlled by the monomermonomer interactions, block compositions and molecular architectures. Templates and patterning for directed selfassembly 5. Enzymatically triggered selfassembly of block copolymers. Block copolymers are normally prepared by controlled polymerization of one monomer, followed by chain extension with a different monomer1 to form ab or abc block copolymers. Selfassembly of block copolymers electronic supplementary information esi yiyong mai and adi eisenberg department of chemistry, mcgill university, 801 sherbrooke street west, montreal, quebec, h3a 2k6, canada email. Moreover, it is one of the most promising techniques for the development of the next generation of nanoelectronic devices and circuits, as it is compatible with current. Nitrile and ethylenevinyl acetate are also copolymers. Directed self assembly dsa is one of the leading candidates for next generation lithography for the semiconductor and data storage. Identifying the nature of surface chemical modification. The threedimensional shape of the dsa feature directly impacts the ability to transfer the dsa pattern into etched patterns.
The material used to make automobile tires is a block copolymer called sbs rubber acrylonitrile butadiene styrene. Creation of guiding patterns for directed selfassembly of. Directed selfassembly of block copolymers for use in bit patterned. Among the many ideas proposed by researchers, directed selfassembly dsa of block copolymers 6, 7, 8, 9, 11, 12, 15, 16, 23, 24 is the most attractive scheme which has been intensively studied, and it is also regarded as a promising newgeneration lithography technique 3, 4, 5, 10. Limits of directed selfassembly in block copolymers. A neutral layer of a brush polymer is directly exposed by electrons, causing the cross. Directed selfassembly of a twostate block copolymer system nano. Directed selfassembly of block copolymers has received a great deal of research attention as a promising nanolithography to complement the intrinsic limitations of conventional photolithography. This unique text discusses the solution self assembly of block copolymers and covers all aspects from basic physical chemistry to applications in soft nanotechnology. Block copolymer bcp nanolithography is widely recognized as a promising complementary approach to circumvent the feature size limits of conventional photolithography. Role of surface softness in directed selfassembly of block copolymers.
Directed selfassembly of block copolymers for nano. Read directed selfassembly of block copolymers for next generation nanolithography on materials today the gateway for polymers and soft materials journal articles. Selfassembly behavior in hydrophilic block copolymers. The implementation of the liunealey line chemoepitaxy flow on 300 mm wafers has allowed the investigation of materials. Modeling directed selfassembly of block copolymers for lithographic applications antoine fouquet. While these approaches offer great control over the triggering process, they all lack the high degree of selectivity that can be achieved by enzymatic activation. Polymersomes with high loading capacity prepared by direct selfassembly of block copolymers in drugs fangyu lin, chihyang cheng, yuhao chuang, shihhuang tung institute of polymer science and engineering, national taiwan university, taipei, 10617, taiwan article info article history. Directed selfassembly of styrenemethyl acrylate block. Block copolymers of ethylene oxide and 1,2butylene oxide c. Directed selfassembly dsa of block copolymers bcps is a chemicalbased complementary alternative to traditional patterning methods providing sub10 nm resolution, lowcost processing and high throughput. Innovative block copolymers for next generation directed selfassembly yukio kawaguchi, terumasa kosaka, toshiyuki himi, tetsuo shimizu, horiba stec,co.
I have examined the final electronic copy of this dissertation for form and content and recommend that it be accepted in partial fulfillment of the requirements for the degree of doctor of philosophy, with a major in chemistry. Directed selfassembly of block copolymers for universal. Received 15 august 2017 received in revised form 9. Polymersomes with high loading capacity prepared by direct. Polyacrylic acidb styrene amphiphilic multiblock copolymers as building. These aggregates provide potential or practical applications in many fields. Selfassembly structures of block copolymers in selective. Directed selfassembly of block copolymers to make bit. Process directed selfassembly of multiblock copolymers. Our website uses cookies cookies enable us to provide the best experience possible and help us understand how visitors use our website. In this work, single chain in mean field simulation methodology was used to study the self assembly of symmetric block copolymers on topographically patterned substrates with sidewall interactions. Block copolymers but not exclusively are interesting because they can microphase separate to form periodic nanostructures, as in the styrenebutadienestyrene block copolymer shown at right.
This hm nl minimizes the number of substrate deposition steps required in graphoepitaxy directed selfassembly dsa process flows. The rapid pattern formation of wellordered block copolymer bcp nanostructures is practical for nextgeneration nanolithography applications. This work examines the pathways for annihilation of defects in symmetric diblock copolymers in the context of directed assembly using patterned substrates. Directed selfassembly of block copolymers is a scalable method to fabricate wellordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Directed selfassembly dsa of block copolymers bcps is a promising approach for the fabrication of sub10 nm features.
Directed selfassembly of block copolymers for nanomanufacturing. Directed selfassembly of block copolymers archived nist. The motivation of this thesis is to study the influence on the selfassembly in water of abb type block copolymers with a hydrophilic of the variation of the hydrophilicity of b from nonsoluble hydrophobic to totally soluble hydrophilic. In this article, we report that a binary solvent vapor annealing methodology. One of the major obstacles to incorporating nanotechnology into everyday products is the difficulty of making nanoscale structures inexpensively over large areas. Block copolymer bcp selfassembly has attracted considerable attention for many decades because it can yield ordered structures in a wide range of morphologies, including spheres, cylinders, bicontinuous structures, lamellae, vesicles, and many other complex or hierarchical assemblies. Front matter ii presentations the following presentations were given during the course of this mphil candidature.
An aim of this book is to bridge the two communities and crossfertilise the different fields. Stanford libraries official online search tool for books, media, journals, databases. Defects in highly ordered selfassembled block copolymers represent an important roadblock toward the adoption of these materials in a wide range of applications. The most attracting feature of block copolymer lithography is the ability to assemble domains into dense arrays of lines or spots with periods and spaces that are. This dissertation explores the use of block copolymers which can selfassemble into different morphologies as templates to fabricate nanostructured materials. His current research interests mainly focus on macromolecular engineering via block copolymer selfassembly in solution and in bulk, and their impact in nanobiotechnologies. Selfassembly of diblock copolymers under confinement. Amphiphilic plgabpolynvinylpyrrolidone pnvp block copolymers have been synthesized via alkyneazide click reaction of it with azideterminated pnvps prepared by raft polymerization of nvp using an azideterminated raft agent. Directed selfassembly of block copolymers for next. Here, we explore the limits of the directed selfassembly of bcps by deliberately adding random imperfections to the template. The threedimensional assembly of poly styrenebmethyl methacrylate psbpmma in chemoepitaxy and graphoepitaxy directed selfassembly dsa was investigated using scanning transmission electron microscopy stem tomography. Although a variety of bcps allow the feature size down to sub10 nm, most of them are incompatible with the existing manufacturing process employed by the microelectronic industry.
Enhancing the directed selfassembly kinetics of block. Magnetic fields are used to create highly aligned hexagonally packed block copolymer cylindrical microdomains with order parameters exceeding 0. Block copolymer bcp selfassembly can generate a range of. Innovative block copolymers for next generation directed. Block copolymers are a class of soft matter that selfassemble to form ordered morphologies at nanometer scales, making them ideal materials for various applications. Understanding the conditions under which defects appear in selfassembling softmatter systems is of great importance, for example, in the development of blockcopolymer bcp nanolithography. We survey well established and newly emerging dsa methods from a tutorial perspective. Block copolymers offer one route to addressing this problem, because they have an intrinsic nanometer length. Block copolymers matyjaszewski polymer group carnegie. Directed selforiented selfassembly of block copolymers using topographical surfaces abstract. Commensurabilitydriven orientation control during block.
In this article, we first summarize the phase behavior of block copolymers in bulk and thin films and some applications for new functional nanomaterials. The tomographic characterization revealed hidden morphologies and defects at the bcp chemical pattern interface in lamellar. Block copolymer bcp selfassembly has attracted considerable attention for many decades because it can yield ordered structures in a wide range of. The use of block copolymers in nanoscale patterning. Directed selforiented selfassembly of block copolymers using topographical surfaces5. A block copolymer change morphology by tuning materials properties block a block b repulsion annealing selfassembly in ordered 2phases structures chainslength n block ratio f segregation strength. Selfassembly of miktoarm starlike ab block copolymers. Marcus mullers publications institut fur theoretische physik. On the origin of the solution behavior of ethyleneoxide containing polymers g. Selective etch removal of material yields nanoporous films which. Crosssectional imaging of directed selfassembly block. Selfassembly of block copolymers for the fabrication of. Selfassembly of miktoarm starlike abn block copolymers. Characterization of buried structure in directed self.
Directed selfassembly of block copolymers and nanostructures, completion seminar, may 2017, the university of melbourne, vic australia. Limits of directed selfassembly in block copolymers nano letters. The first section chapters 24 reports the formation of mesoporous silica films with spherical, cylindrical and bicontinuous pores up to 40 nm in diameter through replicating the morphologies of the solid block. Directed selfassembly of block copolymers for next generation nanolithography. Selfassembly and applications studies in surface science and catalysis alexandridis, p. The polymer is known as kraton and is used for shoe soles and adhesives.
Streamlined etch integration with a unique neutral layer. Directed selforiented selfassembly of block copolymers using topographical surfaces. Defect annihilation pathways in directed assembly of. For more than a decade, block copolymers have garnered significant interest as selfassembling materials for nanoscale patterning. Directed selfassembly of block copolymers is a scalable method to fabricate wellordered patterns over the wafer scale with feature sizes. Block copolymers bcp are selfassembling polymeric materials that have been extensively investigated for several decades. The blocks in sbs rubber are polystyrene and polybutadiene styrenebutatinestyrene. Random copolymer brushes grafted to the background region space between patterns were modeled explicitly.
We present an approach for the creation of guiding patterns to direct the selfassembly of block copolymers. Block copolymers that two or more polymer chains are covalently linked have drawn much attention due to selfassembly into nanometersized morphology such as lamellae, cylinders, spheres, and gyroids. One of the most interesting properties of block copolymers is their ability to selfassemble into numerous morphologies with spatial control on the. Directed self assembly of block copolymers using chemical patterns. Nealey all track directed selfassembly of block copolymers. Block copolymer directed selfassembly bcp dsa is the leading candidate for forming bpm due to its ability to create uniform patterns over macroscopic areas. He received the bronze medal award from the cnrs in 2004 for the work he did on the selfassembly of polypeptidebased block copolymers. Directed selfassembly of block copolymers on chemical patterns. Directed self assembly of block copolymers for nanopatterning nist. Modelling of the selfassembly of block copolymers in selective solvent p. A separate brush layer is replaced by incorporating neutral layer properties into the hardmask to. Directed selfassembly dsa of block copolymers is an effective method to pattern dense arrays of features with dimensions in the nanoscale. Abstract the directed self assembly dsa of block copolymers bcp can multiply or subdivide the pitch of a lithographically defined chemical or topological pattern and is a resolution enhancement candidate to augment conventional. Recent advances have enabled the preparation of new materials with novel self assembling structures, functionality and responsiveness and there have also been concomitant advances.
Recently, alignment of block copolymer domains has been achieved using a topographically patterned substrate with a sidewall preferential to one of the blocks. Directed block copolymer selfassembly implemented via. In this report we introduce the concept of enzymatically triggered selfassembly of block copolymers under physiological conditions. Three dimensional assembly in directed selfassembly of. Modeling directed selfassembly of block copolymers for. 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 wellstudied amphiphiles will prove beneficial to both the surfactant and the polymer communities. However, there remain critical hurdles to achieve the rapid selfassembly of bcps with a high floryhuggins interaction parameter. Directed selfassembly of block copolymers to make bit patterned media inventors paul nealey, guoliang liu, ricardo ruiz, elizabeth dobisz since its founding in 1925 as the patenting and licensing organization for the university of wisconsinmadison, warf has been working with business and industry to transform university research into products.
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