In block copolymer lithography, perpendicularlyoriented cylindrical or lamellar bcp domains are superior to spherical domains for pattern transfer operations due. Directed self oriented self assembly of block copolymers using topographical surfaces5. Relationship between the grafting density of bcp and surface density of hydroxyl moiety on silicon oxide is discussed. Directed selfassembly of highchi block copolymer for. Directed selfassembly dsa methods for block copolymers and. While great progress has been made to implement block copolymer lithography with features in the range of 1020 nm. Selfdirected selfassembly of nanoparticlecopolymer mixtures. Block copolymer bcp nanolithography is widely recognized as a promising complementary approach to circumvent the feature size limits of conventional photolithography. Block copolymer selfassembly in thin films can spontaneously generate periodic nanoscale patterns such as hexagonal arrays of dots or. The directed self assembly dsa method of patterning for microelectronics uses polymer phaseseparation to generate features of less than 20nm, with the positions of self assembling materials externally guided into the desired pattern. Controlled atrp synthesis of novel lineardendritic block. Research on block copolymers bcps has played a critical role in the development of polymer chemistry, with numerous pivotal contributions that have advanced our ability to prepare, characterize, theoretically model, and technologically exploit this class of materials in a myriad of ways in the fields of chemistry, physics, material sciences, and biological and medical sciences.
Defectfree and wellregistered block copolymer domains can be created by directed self assembly on patterned topographic features, known as graphoepitaxy 6,7,8, or on patterns with controlled chemical contrast, known as chemoepitaxy. Xray characterization of directed selfassembly block. Directed self assembly dsa of block copolymers is a promising technology for extending the patterning capability of current lithographic exposure tools. By introducing the heterogeneous nucleation concept to directed selfassembly of block copolymers, the ordering of dynamical process and defect pattern design in thin films of binary blend, ab diblockc homopolymer abc, are investigated by the timedependent ginzburglandau theory and simulated by the cell dynamics simulations. Block copolymer selfassembly provides a platform for fabricating dense, ordered nanostructures by encoding information in the chemical architecture of multicomponent macromolecules. Directed selfassembly of block copolymers for use in bit patterned media fabrication. Our results show that defects emerge due to local shearlike. Selfdirected selfassembly of nanoparticlecopolymer. His current research efforts focus on magnetic field directed selfassembly of functional block copolymer materials and nanoimprint lithography of organic. Directed self assembly of block copolymers for nanomanufacturing 2015, hardcover at the best online prices at ebay. Download it once and read it on your kindle device, pc, phones or tablets.
Published 25 november 20 20 iop publishing ltd journal of physics d. Directed selfassembly of block copolymers on chemical patterns. Limits of directed selfassembly in block copolymers nano. Beginning with a solid overview of the physics and chemistry of block copolymer bcp materials, part 1 covers the synthesis of new materials and. Directed selfassembly of block copolymer, no1 by hiromichi. Directed selfassembly of polystyreneblockpolyacrylic. Directed selfassembly of block copolymer films on atomically. Nanostructured morphologies by selfassembly of diblock. Directed selfassembly of block copolymers for universal. Selfassembly of block copolymers for the fabrication of. Block copolymers offer one route to addressing this problem, because they have an intrinsic nanometer length scale built in.
He has published over 200 papers hindex 56 and edited several books in these areas of polymer research, and organized several. The directed selfassembly dsa method of patterning for microelectronics uses polymer phaseseparation to generate features of less than 20nm, with the positions of selfassembling materials externally guided into the desired pattern. Directed selfassembly of a twostate block copolymer system. On the origin of the solution behavior of ethyleneoxide containing polymers g. Directed self assembly of block copolymers has received a great deal of research attention as a promising nanolithography to complement the intrinsic limitations of conventional photolithography.
Block copolymers bcp are selfassembling polymeric materials that have been extensively investigated for several decades. The block copolymer thin film morphologies therefore offer a genuine. Block copolymer directed selfassembly bcp dsa is the leading candidate for forming bpm due to its ability to create uniform patterns over macroscopic areas. Three dimensional assembly in directed selfassembly of. Directed self assembly of block copolymer bcp is considered as one of the most promising advanced lithography, 1 and can make nanometer scale patterns on the 6inch diameter substrate at the same time without expensive cost, using the self assembly of bcp and guide pattern created by a conventional lithography tool. The directed selfassembly dsa method of patterning for microelectronics uses polymer phaseseparation to generate features of less than 20nm, with the positions of selfassembling materials.
Schematic of highdensity nanowire fabrication in a polymer matrix. Limits of directed selfassembly in block copolymers nano letters. Enabling density multiplication in directed selfassembly. 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 copolymer bcp. Assembly of templatable block copolymers by easily accessible magnetic control. Nanopatterns produced by directed selfassembly in block. Defectfree and wellregistered block copolymer domains can be created by directed selfassembly on patterned topographic features, known as graphoepitaxy 6,7,8, or on patterns with controlled chemical contrast, known as chemoepitaxy. The threedimensional assembly of poly styrenebmethyl methacrylate psbpmma in chemoepitaxy and graphoepitaxy directed selfassembly dsa was investigated using scanning transmission electron microscopy stem tomography. Guiding the selfassembly of block copolymers in 2d and. Recently, directed self assembly dsa of bcps has received enormous research attention from both academia and industry as nextgeneration nanolithography technology.
Directed selfassembly dsa of block copolymers is a promising technology for extending the patterning capability of current lithographic exposure tools. Directed self assembly dsa methods for block copolymers and nanoparticles thin films. Technically, a block is a portion of a macromolecule, comprising many units, that has at least one feature which is not. The tomographic characterization revealed hidden morphologies and defects at the bcp chemical pattern interface in lamellar dsa, and probed the formation of cylinders. Woodhead publishing series in electronic and optical materials. Before sharing sensitive information, make sure youre on a federal government site. 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. Directed selfassembly of block copolymers and nanostructures, completion seminar, may 2017, the university of melbourne, vic australia. Directed selfassembly dsa methods for block copolymers and nanoparticles. Cylinders of p2vp oriented normal to the surface are markedly aligned along the rubbing direction and used as templates to. Block copolymers bcp are self assembling polymeric materials that have been extensively investigated for several decades. Synthesis and directed selfassembly of modified psbpmma. This dissertation explores the use of block copolymers which can selfassemble into different morphologies as templates to fabricate nanostructured materials. Various advanced directed selfassembly approaches are examined, in which block copolymer selfassembly is synergistically integrated with conventional photolithography, such as arf lithography or iline lithography, via either epitaxial selfassembly or the graphoepitaxy principle.
Oct 18, 2000 the second part provides case studies of self assembly in different classes of block copolymers e. Nanodefect management in directed selfassembly of block. Lamellaeforming block copolymers bcps of the hc series showed the ability to form vertically oriented polymer domains. 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. The effect of film thickness and domain spacing on defect densities in directed selfassembly of cylindrical morphology block copolymers, v. Guiding the selfassembly of block copolymers in 2d and 3d. For contact layers that require patterning of cylinders with diameter of tens nanometers, dsa with graphoepitaxy is a good candidate for future nodes. Due to the thermodynamic incompatibility between blocks and the covalent bond among them that avoids macrophase separation, block copolymers can. Directed self assembly dsa of block copolymers bcp is envisaged as an alternative complementary technique that can reduce critical dimension and pitch with high throughput and limited cost 1. Directed self assembly dsa of block copolymers bcps is a promising alternative to advance in miniaturization for the semiconductor industry due to its high resolution and process simplification compared with other approaches. This strategy has been suggested as an option to overcome the patterning resolution challenges facing chemoepitaxy strategies, which utilize chemical stripes with a width of about half the period of block copolymer to orient the. 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.
Directed self assembly of block copolymers for nanomanufacturing woodhead publishing series in electronic and optical materials kindle edition by gronheid, roel, nealey, paul. Directed selfassembly of block copolymers for nanomanufacturing. Directed selfassembly dsa of block copolymers bcps is a promising alternative to advance in miniaturization for the semiconductor industry due to its high resolution and process simplification compared with other approaches. Block copolymers of ethylene oxide and 1,2butylene oxide c. Technically, a block is a portion of a macromolecule, comprising many units, that has at least one feature which is not present in the adjacent portions. Characterization of buried structure in directed self. In particular, line and space using lamellar bcps can be used for the definition of nanowirebased devices. Photothermally directed assembly of block copolymers. Directed selfassembly of block copolymers based on the. Woodhead publishing series in electronic and optical. Directed self assembly of block copolymers for nanomanufacturing. Depending on the volume fraction of the components and chain topology, these macromolecules form a variety of spatially periodic microphases in thermodynamic equilibrium. Controlled atrp synthesis of novel lineardendritic block copolymers and their directed self assembly in breath figure arrays by xin liu 1, tina monzavi 1,2 and ivan gitsov 1,3, 1.
Commensurabilitydriven orientation control during block. The self assembly of block copolymers through microphase separation yields patterns with various morphologies and feature sizes ranging from 3 to 100 nm 1,2,3,4,5. Directed selfassembly of block copolymer, no1 author. Recently, alignment of block copolymer domains has been achieved using a topographically patterned substrate with a sidewall preferential to one of the blocks. While the morphologies that form can be rationalized based on equilibrium arguments, the structures seen experimentally are strongly influenced by kinetic effects. Proceedings paper directed selfassembly of topcoatfree, integrationfriendly highx block copolymers. 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 lithography for patterning sub20 nm features. Introduction directed selfassembly of block copolymer bcp is considered as one of the most promising advanced lithography, 1 and can make nanometer scale patterns on the 6inch diameter substrate at the same time without expensive cost. For example, production of sub40 nm pitch features using 193nm exposure technologies is conceivably possible using dsa methods without relying on time consuming, challenging, and expensive.
Rhys alun griffiths 1,2, aled williams 2, chloe oakland 2, jonathan roberts 2, aravind vijayaraghavan 1 and thomas thomson 1. Directed selfassembly dsachemoepitaxy and graphoepitaxyhas become one of the most appealing nextgeneration lithography techniques, benefiting from. Thin films of cylinderforming asymmetric polystyreneblockpoly2vinylpyridine copolymers s2vps were solvent annealed on the surfaces having the transferred surface pattern to induce their directed selfassembly. By introducing the heterogeneous nucleation concept to directed self assembly of block copolymers, the ordering of dynamical process and defect pattern design in thin films of binary blend, ab diblockc homopolymer abc, are investigated by the timedependent ginzburglandau theory and simulated by the cell dynamics simulations. The detailed annealing process of a few isolated defects.
Phase separated block copolymer particles with tuneable morphologies, 36th australian polymer symposium aps, oral presentation, november 2016, lorne, vic australia. Pattern placement accuracy in block copolymer directed selfassembly based on chemical epitaxy. Directed selfassembly of a twostate block copolymer. In the particular case of magnetic bpm fabrication, directed selfassembly dsa of block copolymers combined with rotary ebeam lithography represents the only currently viable solution to fabricate nanoimprint master templates with feature densities in excess of 1 td in. Directed selfassembly dsa methods for block copolymers. Modelling of the selfassembly of block copolymers in selective solvent p. The psrich and neutral psbpmma block copolymer bcp films were spin coated on the neutral random copolymer hydroxylterminated psrpmma layers grafted on the native oxide and 50 nm thick pecvd amorphous silicon oxide layers. Sep 27, 2018 directed self assembly dsa addresses these issues by using graphoepitaxial 11,12,14 andor chemoepitaxial 15,16,17,18,19 templates, fabricated by conventional lithography techniques, to guide the self assembly of thin films of block copolymers. Directed block copolymer selfassembly implemented via. Directed selfassembly of block copolymers for use in bit.
Directed selfassembly dsa of block copolymers bcps based on topographic patterns is one of the most promising strategies for overcoming resolution limitations in the current lithographic process and fabricating the next generation data storage devices. Directed selfassembly dsa addresses these issues by using graphoepitaxial 11,12,14 andor chemoepitaxial 15,16,17,18,19 templates, fabricated by conventional lithography techniques, to guide the selfassembly of thin films of block copolymers. The conventional organicorganic dsa materials such as polystyreneblockmethyl methacrylate psbpmma have been extensively studied 4,5, however, the low etch contrast between two blocks and the difficulty to. Directed selfassembly of triblock copolymer on chemical.
Dimensional chemical patterns fabricated by electro. Our results show that defects emerge due to local shearlike distortions of the polymertemplate system, a new mechanism that is fundamentally. Recently, directed selfassembly dsa of bcps has received enormous research attention from both academia and industry as nextgeneration nanolithography technology. While the dsa of bcps with deep topographic patterning has been extensively studied both experimentally and theoretically over the past. A possible sequence of repeat units a and b in a triblock copolymer might be aaaaaaabbbbbbbaaaaa. Directed selforiented selfassembly of block copolymers using topographical surfaces5. Directing the selfassembly of block copolymers sciencedirect. 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. Block copolymers comprise two or more homopolymer subunits linked by covalent bonds. Jul 30, 2014 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 lithography for patterning sub20 nm features. Modeling directed selfassembly of block copolymers for. Controlled atrp synthesis of novel lineardendritic block copolymers and their directed selfassembly in breath figure arrays by xin liu 1, tina monzavi 1,2 and ivan gitsov 1,3, 1. Directed selfassembly of highchi block copolymer for nano. Directed self assembly dsa of block copolymers bcps has been expected to become one of the most promising next generation lithography candidates for sub15 nm line patterning and sub20 nm contact hole patterning.
Here, we explore the limits of the directed selfassembly of bcps by deliberately adding random imperfections to the template. Purchase directed self assembly of block copolymers for nanomanufacturing 1st edition. Directed selfassembly of block copolymers archived nist. Directed self assembly dsa is one of the leading candidates for next generation lithography for the semiconductor and data storage. Directed selfassembly dsa of block copolymers bcps is a leading strategy to pattern at sublithographic resolution in the technology roadmap for semiconductors and is the only known solution to fabricate nanoimprint templates for the production of bit pattern media. Directed selfassembly of asymmetric block copolymers in thin. The directed selfassembly dsa of block copolymers has attracted a great deal of interest due to its potential applications in sub10 nm lithography. Key laboratory of molecular engineering of polymer department of macromolecular science, fudan university, shanghai, 200438 china. Directed selfassembly of a twostate block copolymer system nano. Directed selfassembly of block copolymers for next. Oxidation nanolithography ji xu department of polymer science and engineering university of massachusetts amherst 120 governors drive, amherst ma 01003 usa.
Directed self assembly of block copolymers for nanopatterning nist. The directed self assembly dsa method of patterning for microelectronics uses polymer phaseseparation to generate features of less than 20nm, with the positions of self assembling materials. Directed self assembly of block copolymers using chemical. This article provides a brief introduction to i the spontaneous and directed selfassembly of bcps, ii. Fundamentals and applications alamgir karim dow chair professor department of chemical and biomolecular engineering university of houston, tx 77004 abstract facile directed self assembly dsa of multicomponent thin films is important. Directed selfassembly of block copolymers for nano. The selfassembly of block copolymers through microphase separation yields patterns with various morphologies and feature sizes ranging from 3 to 100 nm 1,2,3,4,5. Directed selfassembly of asymmetric block copolymers in. Understanding the conditions under which defects appear in selfassembling softmatter systems is of great importance, for example, in the development of blockcopolymer bcp nanolithography.
The union of the homopolymer subunits may require an intermediate nonrepeating subunit, known as a junction block. These aggregates provide potential or practical applications in many fields. The goal of this project is to develop new techniques to control and characterize the behavior of diblock copolymers for use in integrated circuit and data storage applications. Purchase directed selfassembly of block copolymers for nanomanufacturing 1st edition. Directed selfassembly of block copolymers for use in bit patterned. Thin films of cylinderforming asymmetric polystyrene block poly2vinylpyridine copolymers s2vps were solvent annealed on the surfaces having the transferred surface pattern to induce their directed self assembly.
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