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Title: Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends

Journal Article · · ACS Nano

The ubiquitous presence of thermodynamically unfavored but kinetically trapped topological defects in nanopatterns formed via self-assembly of block copolymer thin films may prevent their use for many envisioned applications. Here, we demonstrate that lamellae patterns formed by symmetric polystyrene-block-poly(methyl methacrylate) diblock copolymers self-assemble and order extremely rapidly when the diblock copolymers are blended with low molecular weight homopolymers of the constituent blocks. Being in the “wet brush” regime, the homopolymers uniformly distribute within their respective self-assembled microdomains, preventing increases in domain widths. An order-of-magnitude increase in topological grain size in blends over the neat (unblended) diblock copolymer is achieved within minutes of thermal annealing as a result of the significantly higher power law exponent for ordering kinetics in the blends. Moreover, the blends are demonstrated to be capable of rapid and robust domain alignment within micrometer-scale trenches, in contrast to the corresponding neat diblock copolymer. Furthermore, these results can be attributed to the lowering of energy barriers associated with domain boundaries by bringing the system closer to an order–disorder transition through low molecular weight homopolymer blending.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1413958
Report Number(s):
BNL--114813-2017-JA; KC0403020
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 12 Vol. 11; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (70)

Graphoepitaxy of Spherical Domain Block Copolymer Films journal August 2001
Spontaneous Lamellar Alignment in Thickness-Modulated Block Copolymer Films journal August 2009
Eliminating the Trade-Off between the Throughput and Pattern Quality of Sub-15 nm Directed Self-Assembly via Warm Solvent Annealing journal November 2014
Ultrafast Assembly of PS-PDMS Block Copolymers on 300 mm Wafers by Blending with Plasticizers journal June 2016
Macroscopic Orientation of Block Copolymer Cylinders in Single-Layer Films by Shearing journal October 2004
Dense Self-Assembly on Sparse Chemical Patterns: Rectifying and Multiplying Lithographic Patterns Using Block Copolymers journal August 2008
Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers journal September 2010
Robust Superhydrophobicity in Large-Area Nanostructured Surfaces Defined by Block-Copolymer Self Assembly journal October 2013
Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning journal June 2017
Experimental investigation of collagen waviness and orientation in the arterial adventitia using confocal laser scanning microscopy journal July 2011
Directing the self-assembly of block copolymers journal October 2007
Block Copolymer Response to Photothermal Stress Fields journal June 2015
Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films journal July 2015
Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing journal July 2016
The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-forming Liquids journal July 1955
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment journal December 2010
Ordered structure in mixtures of a block copolymer and homopolymers. 1. Solubilization of low molecular weight homopolymers journal January 1991
Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight journal November 1991
Interfacial segregation in two-phase polymer blends with diblock copolymer additives: the effect of homopolymer molecular weight journal January 1992
Diffusion in Block Copolymer Melts: The Disordered Region and the Vicinity of the Order-Disorder Transition journal June 1994
Phase Behavior of Block Copolymer/Homopolymer Blends journal August 1995
Effect of homopolymer molecular weight on the morphology of block copolymer/homopolymer blends journal June 1987
Molecular weight and polydispersity effects at polymer-polymer interfaces journal January 1990
Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate) journal May 1990
Composition and Temperature Dependence of Monomer Friction in Polystyrene/Poly(methyl methacrylate) Matrices journal July 2001
Ordered Structures and Phase Transitions in Mixtures of a Polystyrene/Polyisoprene Block Copolymer with the Corresponding Homopolymers in Thin Films and in Bulk journal May 2004
Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects journal July 2012
Chemical Patterns for Directed Self-Assembly of Lamellae-Forming Block Copolymers with Density Multiplication of Features journal February 2013
Solvent Vapor Annealing of Block Polymer Thin Films journal June 2013
Visualization of Individual Defect Mobility and Annihilation within Cylinder-Forming Diblock Copolymer Thin Films on Nanopatterned Substrates journal October 2013
Retardation of Grain Growth and Grain Boundary Pinning in Athermal Block Copolymer Blend Systems journal February 2014
Phase Behavior and Dimensional Scaling of Symmetric Block Copolymer−Homopolymer Ternary Blends in Thin Films journal April 2009
Dimensional Scaling of Cylinders in Thin Films of Block Copolymer−Homopolymer Ternary Blends journal July 2009
Lamellar Domain Spacings of Diblock Copolymer/Homopolymer Blends and Conformations of Block Chains in Their Microdomains journal September 1997
Anomalous Rapid Defect Annihilation in Self-Assembled Nanopatterns by Defect Melting journal January 2015
A Path to Ultranarrow Patterns Using Self-Assembled Lithography journal March 2010
Ultralarge-Area Block Copolymer Lithography Enabled by Disposable Photoresist Prepatterning journal August 2010
Fast Assembly of Ordered Block Copolymer Nanostructures through Microwave Annealing journal October 2010
Pattern Placement Accuracy in Block Copolymer Directed Self-Assembly Based on Chemical Epitaxy journal December 2012
Chemically Enhancing Block Copolymers for Block-Selective Synthesis of Self-Assembled Metal Oxide Nanostructures journal December 2012
Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films journal October 2012
Directed Assembly of High Molecular Weight Block Copolymers: Highly Ordered Line Patterns of Perpendicularly Oriented Lamellae with Large Periods journal March 2013
Deconvoluting the Mechanism of Microwave Annealing of Block Copolymer Thin Films journal March 2014
Two-Dimensional Pattern Formation Using Graphoepitaxy of PS- b -PMMA Block Copolymers for Advanced FinFET Device and Circuit Fabrication journal April 2014
Deep-Nanoscale Pattern Engineering by Immersion-Induced Self-Assembly journal October 2014
Millisecond Ordering of Block Copolymer Films via Photothermal Gradients journal February 2015
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries journal October 2007
Electric Field Alignment of a Block Copolymer Nanopattern: Direct Observation of the Microscopic Mechanism journal April 2009
Selective directed self-assembly of coexisting morphologies using block copolymer blends journal August 2016
Enabling complex nanoscale pattern customization using directed self-assembly journal December 2014
Sub-50-nm self-assembled nanotextures for enhanced broadband antireflection in silicon solar cells journal January 2015
Nanostructure engineering by templated self-assembly of block copolymers journal October 2004
Evolution of block-copolymer order through a moving thermal zone journal January 2010
Ordering dynamics in symmetric PS-b-PMMA diblock copolymer thin films during rapid thermal processing journal January 2014
The Thermodynamics of High Polymer Solutions. V. Phase Equilibria in the Ternary System: Polymer 1—Polymer 2—Solvent journal March 1949
Self-aligned self assembly of multi-nanowire silicon field effect transistors journal October 2005
Bit patterned media based on block copolymer directed assembly with narrow magnetic switching field distribution journal February 2010
Phase equilibria in copolymer/homopolymer ternary blends: Molecular weight effects journal August 1990
Molecular pathways for defect annihilation in directed self-assembly journal October 2015
Rapid ordering of block copolymer thin films journal August 2016
Effect of structural anisotropy on the coarsening kinetics of diblock copolymer striped patterns journal February 2008
Ordering mechanisms in two-dimensional sphere-forming block copolymers journal June 2005
Polymeric Bicontinuous Microemulsions journal August 1997
Bit-Patterned Magnetic Recording: Theory, Media Fabrication, and Recording Performance journal May 2015
Defect source analysis of directed self-assembly process journal July 2013
Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures journal June 2005
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly journal August 2008
Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates journal August 2008
Mechanisms of Ordering in Striped Patterns journal November 2000
Polymer self assembly in semiconductor microelectronics journal September 2007

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