Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends
Abstract
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.
- Authors:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1413958
- Report Number(s):
- BNL-114813-2017-JA
Journal ID: ISSN 1936-0851; KC0403020; TRN: US1800606
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; block copolymer; directed self-assembly; homopolymer; coarsening kinetics; ternary blends; Center for Functional Nanomaterials; pattern transfer
Citation Formats
Doerk, Gregory S., and Yager, Kevin G. Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends. United States: N. p., 2017.
Web. doi:10.1021/acsnano.7b06154.
Doerk, Gregory S., & Yager, Kevin G. Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends. United States. https://doi.org/10.1021/acsnano.7b06154
Doerk, Gregory S., and Yager, Kevin G. Fri .
"Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends". United States. https://doi.org/10.1021/acsnano.7b06154. https://www.osti.gov/servlets/purl/1413958.
@article{osti_1413958,
title = {Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends},
author = {Doerk, Gregory S. and Yager, Kevin G.},
abstractNote = {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.},
doi = {10.1021/acsnano.7b06154},
journal = {ACS Nano},
number = 12,
volume = 11,
place = {United States},
year = {2017},
month = {12}
}
Web of Science
Works referenced in this record:
Self-aligned self assembly of multi-nanowire silicon field effect transistors
journal, October 2005
- Black, C. T.
- Applied Physics Letters, Vol. 87, Issue 16
Two-Dimensional Pattern Formation Using Graphoepitaxy of PS- b -PMMA Block Copolymers for Advanced FinFET Device and Circuit Fabrication
journal, April 2014
- Tsai, Hsinyu; Pitera, Jed W.; Miyazoe, Hiroyuki
- ACS Nano, Vol. 8, Issue 5
Bit patterned media based on block copolymer directed assembly with narrow magnetic switching field distribution
journal, February 2010
- Hellwig, O.; Bosworth, J. K.; Dobisz, E.
- Applied Physics Letters, Vol. 96, Issue 5
Bit-Patterned Magnetic Recording: Theory, Media Fabrication, and Recording Performance
journal, May 2015
- Albrecht, Thomas R.; Arora, Hitesh; Ayanoor-Vitikkate, Vipin
- IEEE Transactions on Magnetics, Vol. 51, Issue 5
Sub-50-nm self-assembled nanotextures for enhanced broadband antireflection in silicon solar cells
journal, January 2015
- Rahman, Atikur; Ashraf, Ahsan; Xin, Huolin
- Nature Communications, Vol. 6, Issue 1
Robust Superhydrophobicity in Large-Area Nanostructured Surfaces Defined by Block-Copolymer Self Assembly
journal, October 2013
- Checco, Antonio; Rahman, Atikur; Black, Charles T.
- Advanced Materials, Vol. 26, Issue 6
Directing the self-assembly of block copolymers
journal, October 2007
- Darling, S. B.
- Progress in Polymer Science, Vol. 32, Issue 10
Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects
journal, July 2012
- Takahashi, Hassei; Laachi, Nabil; Delaney, Kris T.
- Macromolecules, Vol. 45, Issue 15
Molecular pathways for defect annihilation in directed self-assembly
journal, October 2015
- Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 46
Macroscopic Orientation of Block Copolymer Cylinders in Single-Layer Films by Shearing
journal, October 2004
- Angelescu, D. E.; Waller, J. H.; Adamson, D. H.
- Advanced Materials, Vol. 16, Issue 19
Electric Field Alignment of a Block Copolymer Nanopattern: Direct Observation of the Microscopic Mechanism
journal, April 2009
- Olszowka, Violetta; Hund, Markus; Kuntermann, Volker
- ACS Nano, Vol. 3, Issue 5
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment
journal, December 2010
- Majewski, Pawel W.; Gopinadhan, Manesh; Jang, Woo-Sik
- Journal of the American Chemical Society, Vol. 132, Issue 49
Evolution of block-copolymer order through a moving thermal zone
journal, January 2010
- Yager, Kevin G.; Fredin, Nathaniel J.; Zhang, Xiaohua
- Soft Matter, Vol. 6, Issue 1
Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films
journal, October 2012
- Singh, Gurpreet; Yager, Kevin G.; Berry, Brian
- ACS Nano, Vol. 6, Issue 11
Dense Self-Assembly on Sparse Chemical Patterns: Rectifying and Multiplying Lithographic Patterns Using Block Copolymers
journal, August 2008
- Cheng, Joy Y.; Rettner, Charles T.; Sanders, Daniel P.
- Advanced Materials, Vol. 20, Issue 16
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly
journal, August 2008
- Ruiz, R.; Kang, H.; Detcheverry, F. A.
- Science, Vol. 321, Issue 5891
Chemical Patterns for Directed Self-Assembly of Lamellae-Forming Block Copolymers with Density Multiplication of Features
journal, February 2013
- Liu, Chi-Chun; Ramírez-Hernández, Abelardo; Han, Eungnak
- Macromolecules, Vol. 46, Issue 4
Pattern Placement Accuracy in Block Copolymer Directed Self-Assembly Based on Chemical Epitaxy
journal, December 2012
- Doerk, Gregory S.; Liu, Chi-Chun; Cheng, Joy Y.
- ACS Nano, Vol. 7, Issue 1
Nanostructure engineering by templated self-assembly of block copolymers
journal, October 2004
- Cheng, Joy Y.; Mayes, Anne M.; Ross, Caroline A.
- Nature Materials, Vol. 3, Issue 11
Graphoepitaxy of Spherical Domain Block Copolymer Films
journal, August 2001
- Segalman, R. A.; Yokoyama, H.; Kramer, E. J.
- Advanced Materials, Vol. 13, Issue 15, p. 1152-1155
Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates
journal, August 2008
- Bita, I.; Yang, J. K. W.; Jung, Y. S.
- Science, Vol. 321, Issue 5891
A Path to Ultranarrow Patterns Using Self-Assembled Lithography
journal, March 2010
- Jung, Yeon Sik; Chang, J. B.; Verploegen, Eric
- Nano Letters, Vol. 10, Issue 3
Defect source analysis of directed self-assembly process
journal, July 2013
- Delgadillo, Paulina Rincon; Suri, Mayur; Durant, Stephane
- Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 12, Issue 3
Solvent Vapor Annealing of Block Polymer Thin Films
journal, June 2013
- Sinturel, Christophe; Vayer, Marylène; Morris, Michael
- Macromolecules, Vol. 46, Issue 14
Directed Assembly of High Molecular Weight Block Copolymers: Highly Ordered Line Patterns of Perpendicularly Oriented Lamellae with Large Periods
journal, March 2013
- Kim, Eunhye; Ahn, Hyungju; Park, Sungmin
- ACS Nano, Vol. 7, Issue 3
Eliminating the Trade-Off between the Throughput and Pattern Quality of Sub-15 nm Directed Self-Assembly via Warm Solvent Annealing
journal, November 2014
- Kim, Jong Min; Kim, YongJoo; Park, Woon Ik
- Advanced Functional Materials, Vol. 25, Issue 2
Deep-Nanoscale Pattern Engineering by Immersion-Induced Self-Assembly
journal, October 2014
- Park, Woon Ik; Kim, Jong Min; Jeong, Jae Won
- ACS Nano, Vol. 8, Issue 10
Ordering dynamics in symmetric PS-b-PMMA diblock copolymer thin films during rapid thermal processing
journal, January 2014
- Perego, Michele; Ferrarese Lupi, Federico; Ceresoli, Monica
- J. Mater. Chem. C, Vol. 2, Issue 32
Fast Assembly of Ordered Block Copolymer Nanostructures through Microwave Annealing
journal, October 2010
- Zhang, Xiaojiang; Harris, Kenneth D.; Wu, Nathanael L. Y.
- ACS Nano, Vol. 4, Issue 11
Deconvoluting the Mechanism of Microwave Annealing of Block Copolymer Thin Films
journal, March 2014
- Jin, Cong; Murphy, Jeffrey N.; Harris, Kenneth D.
- ACS Nano, Vol. 8, Issue 4
Millisecond Ordering of Block Copolymer Films via Photothermal Gradients
journal, February 2015
- Majewski, Pawel W.; Yager, Kevin G.
- ACS Nano, Vol. 9, Issue 4
Block Copolymer Response to Photothermal Stress Fields
journal, June 2015
- Majewski, Pawel W.; Yager, Kevin G.
- Macromolecules, Vol. 48, Issue 13
Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films
journal, July 2015
- Majewski, Pawel W.; Yager, Kevin G.
- Nano Letters, Vol. 15, Issue 8
Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning
journal, June 2017
- Jin, Hyeong Min; Park, Dae Yong; Jeong, Seong-Jun
- Advanced Materials, Vol. 29, Issue 32
Ultrafast Assembly of PS-PDMS Block Copolymers on 300 mm Wafers by Blending with Plasticizers
journal, June 2016
- Arias-Zapata, Javier; Böhme, Sophie; Garnier, Jérôme
- Advanced Functional Materials, Vol. 26, Issue 31
Anomalous Rapid Defect Annihilation in Self-Assembled Nanopatterns by Defect Melting
journal, January 2015
- Kim, Bong Hoon; Park, So Jung; Jin, Hyeong Min
- Nano Letters, Vol. 15, Issue 2
Phase Behavior and Dimensional Scaling of Symmetric Block Copolymer−Homopolymer Ternary Blends in Thin Films
journal, April 2009
- Liu, Guoliang; Stoykovich, Mark P.; Ji, Shengxiang
- Macromolecules, Vol. 42, Issue 8
Dimensional Scaling of Cylinders in Thin Films of Block Copolymer−Homopolymer Ternary Blends
journal, July 2009
- Stuen, Karl O.; Thomas, Carla S.; Liu, Guoliang
- Macromolecules, Vol. 42, Issue 14
Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures
journal, June 2005
- Stoykovich, Mark P.; Müller, Marcus; Kim, Sang Ouk
- Science, Vol. 308, Issue 5727, p. 1442-1446
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries
journal, October 2007
- Stoykovich, Mark P.; Kang, Huiman; Daoulas, Kostas Ch.
- ACS Nano, Vol. 1, Issue 3
Interfacial segregation in two-phase polymer blends with diblock copolymer additives: the effect of homopolymer molecular weight
journal, January 1992
- Dai, Kevin H.; Kramer, Edward J.; Shull, Kenneth R.
- Macromolecules, Vol. 25, Issue 1
Polymer self assembly in semiconductor microelectronics
journal, September 2007
- Black, C. T.; Ruiz, R.; Breyta, G.
- IBM Journal of Research and Development, Vol. 51, Issue 5
Ordered structure in mixtures of a block copolymer and homopolymers. 1. Solubilization of low molecular weight homopolymers
journal, January 1991
- Tanaka, Hideaki; Hasegawa, Hirokazu; Hashimoto, Takeji
- Macromolecules, Vol. 24, Issue 1
Lamellar Domain Spacings of Diblock Copolymer/Homopolymer Blends and Conformations of Block Chains in Their Microdomains
journal, September 1997
- Torikai, Naoya; Takabayashi, Naomi; Noda, Ichiro
- Macromolecules, Vol. 30, Issue 19
Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight
journal, November 1991
- Winey, Karen I.; Thomas, Edwin L.; Fetters, Lewis J.
- Macromolecules, Vol. 24, Issue 23
Effect of homopolymer molecular weight on the morphology of block copolymer/homopolymer blends
journal, June 1987
- Quan, X.; Gancarz, I.; Koberstein, J. T.
- Macromolecules, Vol. 20, Issue 6
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
- Mykhaylyk, Tetyana A.; Mykhaylyk, Oleksandr O.; Collins, Stephen
- Macromolecules, Vol. 37, Issue 9
Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995
- Matsen, M. W.
- Macromolecules, Vol. 28, Issue 17
Effect of structural anisotropy on the coarsening kinetics of diblock copolymer striped patterns
journal, February 2008
- Ruiz, R.; Bosworth, J. K.; Black, C. T.
- Physical Review B, Vol. 77, Issue 5
Rapid ordering of block copolymer thin films
journal, August 2016
- Majewski, Pawel W.; Yager, Kevin G.
- Journal of Physics: Condensed Matter, Vol. 28, Issue 40
Spontaneous Lamellar Alignment in Thickness-Modulated Block Copolymer Films
journal, August 2009
- Kim, Bong Hoon; Lee, Hyung Min; Lee, Joo-Hyung
- Advanced Functional Materials, Vol. 19, Issue 16
Mechanisms of Ordering in Striped Patterns
journal, November 2000
- Harrison, C.
- Science, Vol. 290, Issue 5496
Composition and Temperature Dependence of Monomer Friction in Polystyrene/Poly(methyl methacrylate) Matrices
journal, July 2001
- Milhaupt, Jodi M.; Lodge, Timothy P.; Smith, Steven D.
- Macromolecules, Vol. 34, Issue 16
Visualization of Individual Defect Mobility and Annihilation within Cylinder-Forming Diblock Copolymer Thin Films on Nanopatterned Substrates
journal, October 2013
- Tong, Qianqian; Sibener, S. J.
- Macromolecules, Vol. 46, Issue 21
The Temperature Dependence of Relaxation Mechanisms in Amorphous Polymers and Other Glass-forming Liquids
journal, July 1955
- Williams, Malcolm L.; Landel, Robert F.; Ferry, John D.
- Journal of the American Chemical Society, Vol. 77, Issue 14
Ordering mechanisms in two-dimensional sphere-forming block copolymers
journal, June 2005
- Vega, Daniel A.; Harrison, Christopher K.; Angelescu, Dan E.
- Physical Review E, Vol. 71, Issue 6
The Thermodynamics of High Polymer Solutions. V. Phase Equilibria in the Ternary System: Polymer 1—Polymer 2—Solvent
journal, March 1949
- Scott, Robert L.
- The Journal of Chemical Physics, Vol. 17, Issue 3
Phase equilibria in copolymer/homopolymer ternary blends: Molecular weight effects
journal, August 1990
- Broseta, Daniel; Fredrickson, Glenn H.
- The Journal of Chemical Physics, Vol. 93, Issue 4
Polymeric Bicontinuous Microemulsions
journal, August 1997
- Bates, Frank S.; Maurer, Wayne W.; Lipic, Paul M.
- Physical Review Letters, Vol. 79, Issue 5
Molecular weight and polydispersity effects at polymer-polymer interfaces
journal, January 1990
- Broseta, Daniel; Fredrickson, Glenn H.; Helfand, Eugene
- Macromolecules, Vol. 23, Issue 1
Diffusion in Block Copolymer Melts: The Disordered Region and the Vicinity of the Order-Disorder Transition
journal, June 1994
- Dalvi, M. C.; Lodge, T. P.
- Macromolecules, Vol. 27, Issue 13
Retardation of Grain Growth and Grain Boundary Pinning in Athermal Block Copolymer Blend Systems
journal, February 2014
- Ryu, Hyung Ju; Sun, Jane; Avgeropoulos, Apostolos
- Macromolecules, Vol. 47, Issue 4
Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate)
journal, May 1990
- Russell, Thomas P.; Hjelm, Rex P.; Seeger, Phil A.
- Macromolecules, Vol. 23, Issue 3
Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing
journal, July 2016
- Xiong, Shisheng; Wan, Lei; Ishida, Yoshihito
- ACS Nano, Vol. 10, Issue 8
Chemically Enhancing Block Copolymers for Block-Selective Synthesis of Self-Assembled Metal Oxide Nanostructures
journal, December 2012
- Kamcev, Jovan; Germack, David S.; Nykypanchuk, Dmytro
- ACS Nano, Vol. 7, Issue 1
Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers
journal, September 2010
- Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
- Advanced Materials, Vol. 22, Issue 45, p. 5129-5133
Enabling complex nanoscale pattern customization using directed self-assembly
journal, December 2014
- Doerk, Gregory S.; Cheng, Joy Y.; Singh, Gurpreet
- Nature Communications, Vol. 5, Issue 1
Selective directed self-assembly of coexisting morphologies using block copolymer blends
journal, August 2016
- Stein, A.; Wright, G.; Yager, K. G.
- Nature Communications, Vol. 7, Issue 1
Experimental investigation of collagen waviness and orientation in the arterial adventitia using confocal laser scanning microscopy
journal, July 2011
- Rezakhaniha, R.; Agianniotis, A.; Schrauwen, J. T. C.
- Biomechanics and Modeling in Mechanobiology, Vol. 11, Issue 3-4
Ultralarge-Area Block Copolymer Lithography Enabled by Disposable Photoresist Prepatterning
journal, August 2010
- Jeong, Seong-Jun; Moon, Hyoung-Seok; Kim, Bong Hoon
- ACS Nano, Vol. 4, Issue 9
Works referencing / citing this record:
Nanostructure stability and swelling of ternary block copolymer/homopolymer blends: A direct comparison between dissipative particle dynamics and experiment
journal, April 2019
- Goodson, Amy D.; Liu, Guoliang; Rick, Maxwell S.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 12
Electrospray deposition tool: Creating compositionally gradient libraries of nanomaterials
journal, January 2020
- Toth, Kristof; Osuji, Chinedum O.; Yager, Kevin G.
- Review of Scientific Instruments, Vol. 91, Issue 1
Photothermally Directed Assembly of Block Copolymers
journal, December 2019
- Nowak, Samantha R.; Yager, Kevin G.
- Advanced Materials Interfaces, Vol. 7, Issue 5
Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends: Thin Film Confinement Reduces Compatibility in Symmetric Ternary Block Copolymer/Homopolymer Blends
journal, September 2018
- Uddin, Md Fakar; Jiang, Zhang; Raymond, Andrew
- Journal of Polymer Science Part B: Polymer Physics, Vol. 56, Issue 21
A Kriging-Based Approach to Autonomous Experimentation with Applications to X-Ray Scattering
journal, August 2019
- Noack, Marcus M.; Yager, Kevin G.; Fukuto, Masafumi
- Scientific Reports, Vol. 9, Issue 1