Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends
Abstract
The slow kinetics of block copolymer self-assembly may hinder, or even prevent, the realization of expected equilibrium ordered morphologies. Here in this paper we investigate the self-assembly kinetics of cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and its corresponding ternary blends with low molecular weight PS and PMMA in thin films ranging from <1 to several cylinder layers in thickness. In situ grazing-incidence X-ray scattering coupled with ex situ electron microscopy reveals pathway-dependent ordering substantially altered by homopolymer blending. In particular, the neat (unblended) block copolymer (BCP) is kinetically frustrated in films more than ~1 cylinder layer thick and is unable to reach a state of ordered hexagonally packed cylinders during the annealing interval. On the other hand, while blends exhibit similar pattern coarsening behavior to neat BCPs for hexagonally ordered cylinders, reorientation transitions between vertical or horizontal cylinders are dramatically accelerated in blend thin films. We infer that more rapid early stage ordering observed in blends can be attributed in part to faster reorientation transitions.
- Authors:
-
[1];
[1]
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- City College of City Univ. of New York, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1767427
- Alternate Identifier(s):
- OSTI ID: 1485805
- Report Number(s):
- BNL-221092-2021-JAAM; BNL-209683-2018-JAAM
Journal ID: ISSN 0024-9297
- Grant/Contract Number:
- SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 24; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; Thickness; thin films; grazing incidence small angle scattering; homopolymers; annealing (metallurgy)
Citation Formats
Doerk, Gregory S., Li, Ruipeng, Fukuto, Masafumi, Rodriguez, Alfredo, and Yager, Kevin G. Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends. United States: N. p., 2018.
Web. doi:10.1021/acs.macromol.8b01773.
Doerk, Gregory S., Li, Ruipeng, Fukuto, Masafumi, Rodriguez, Alfredo, & Yager, Kevin G. Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends. United States. https://doi.org/10.1021/acs.macromol.8b01773
Doerk, Gregory S., Li, Ruipeng, Fukuto, Masafumi, Rodriguez, Alfredo, and Yager, Kevin G. Wed .
"Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends". United States. https://doi.org/10.1021/acs.macromol.8b01773. https://www.osti.gov/servlets/purl/1767427.
@article{osti_1767427,
title = {Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends},
author = {Doerk, Gregory S. and Li, Ruipeng and Fukuto, Masafumi and Rodriguez, Alfredo and Yager, Kevin G.},
abstractNote = {The slow kinetics of block copolymer self-assembly may hinder, or even prevent, the realization of expected equilibrium ordered morphologies. Here in this paper we investigate the self-assembly kinetics of cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) and its corresponding ternary blends with low molecular weight PS and PMMA in thin films ranging from <1 to several cylinder layers in thickness. In situ grazing-incidence X-ray scattering coupled with ex situ electron microscopy reveals pathway-dependent ordering substantially altered by homopolymer blending. In particular, the neat (unblended) block copolymer (BCP) is kinetically frustrated in films more than ~1 cylinder layer thick and is unable to reach a state of ordered hexagonally packed cylinders during the annealing interval. On the other hand, while blends exhibit similar pattern coarsening behavior to neat BCPs for hexagonally ordered cylinders, reorientation transitions between vertical or horizontal cylinders are dramatically accelerated in blend thin films. We infer that more rapid early stage ordering observed in blends can be attributed in part to faster reorientation transitions.},
doi = {10.1021/acs.macromol.8b01773},
journal = {Macromolecules},
number = 24,
volume = 51,
place = {United States},
year = {Wed Dec 12 00:00:00 EST 2018},
month = {Wed Dec 12 00:00:00 EST 2018}
}
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Works referenced in this record:
Self-assembled nanotextures impart broadband transparency to glass windows and solar cell encapsulants
journal, October 2017
- Liapis, Andreas C.; Rahman, Atikur; Black, Charles T.
- Applied Physics Letters, Vol. 111, Issue 18
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
Self-Diffusion and Tracer Diffusion in Sphere-Forming Block Copolymers
journal, September 2003
- Cavicchi, Kevin A.; Lodge, Timothy P.
- Macromolecules, Vol. 36, Issue 19
Scaling of correlation length in lamellae forming PS-b-PMMA thin films upon high temperature rapid thermal treatments
journal, January 2015
- Ceresoli, M.; Volpe, F. G.; Seguini, G.
- Journal of Materials Chemistry C, Vol. 3, Issue 33
Pathway-engineering for highly-aligned block copolymer arrays
journal, January 2018
- Choo, Youngwoo; Majewski, Paweł W.; Fukuto, Masafumi
- Nanoscale, Vol. 10, Issue 1
Hexagonal phase ordering in strongly segregated copolymer films
journal, October 2015
- Glasner, Karl
- Physical Review E, Vol. 92, Issue 4
Reordering transitions during annealing of block copolymer cylinder phases
journal, January 2016
- Majewski, Pawel W.; Yager, Kevin G.
- Soft Matter, Vol. 12, Issue 1
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
Asymmetric superstructure formed in a block copolymer via phase separation
journal, November 2007
- Peinemann, Klaus-Viktor; Abetz, Volker; Simon, Peter F. W.
- Nature Materials, Vol. 6, Issue 12
A Route to Nanoscopic Materials via Sequential Infiltration Synthesis on Block Copolymer Templates
journal, May 2011
- Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
- ACS Nano, Vol. 5, Issue 6, p. 4600-4606
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
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
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
Diffusion of block copolymers
journal, October 2006
- Yokoyama, Hideaki
- Materials Science and Engineering: R: Reports, Vol. 53, Issue 5-6
Microdomain Orientation of PS- b -PMMA by Controlled Interfacial Interactions
journal, September 2008
- Ham, Sujin; Shin, Changhak; Kim, Eunhye
- Macromolecules, Vol. 41, 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
Ordering kinetics in two-dimensional hexagonal pattern of cylinder-forming PS- -PMMA block copolymer thin films: Dependence on the segregation strength
journal, May 2018
- Seguini, Gabriele; Zanenga, Fabio; Laus, Michele
- Physical Review Materials, Vol. 2, Issue 5
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
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
Thermally Switchable Aligned Nanopores by Magnetic-Field Directed Self-Assembly of Block Copolymers
journal, June 2014
- Gopinadhan, Manesh; Deshmukh, Prashant; Choo, Youngwoo
- Advanced Materials, Vol. 26, Issue 30
Weakly Nonlinear Theory of Grain Boundary Motion in Patterns with Crystalline Symmetry
journal, July 2002
- Boyer, Denis; Viñals, Jorge
- Physical Review Letters, Vol. 89, Issue 5
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
Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions
journal, July 2009
- Han, Eungnak; Stuen, Karl O.; Leolukman, Melvina
- Macromolecules, Vol. 42, Issue 13
Domain Orientation and Grain Coarsening in Cylinder-Forming Poly(styrene- b -methyl methacrylate) Films
journal, June 2011
- Ji, Shengxiang; Liu, Chi-Chun; Liao, Wen
- Macromolecules, Vol. 44, Issue 11
Millisecond Ordering of Block Copolymer Films via Photothermal Gradients
journal, February 2015
- Majewski, Pawel W.; Yager, Kevin G.
- ACS Nano, Vol. 9, Issue 4
Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing
journal, August 2012
- Singh, Gurpreet; Yager, Kevin G.; Smilgies, Detlef-M.
- Macromolecules, Vol. 45, Issue 17
Beyond native block copolymer morphologies
journal, January 2017
- Doerk, Gregory S.; Yager, Kevin G.
- Molecular Systems Design & Engineering, Vol. 2, Issue 5
Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends
journal, October 2016
- Doerk, Gregory S.; Yager, Kevin G.
- ACS Nano, Vol. 11, Issue 12
Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995
- Matsen, M. W.
- Macromolecules, Vol. 28, Issue 17
Block Copolymer Response to Photothermal Stress Fields
journal, June 2015
- Majewski, Pawel W.; Yager, Kevin G.
- Macromolecules, Vol. 48, Issue 13
Non-native three-dimensional block copolymer morphologies
journal, December 2016
- Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory
- Nature Communications, Vol. 7, Issue 1
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
Dynamics of pattern coarsening in a two-dimensional smectic system
journal, July 2002
- Harrison, Christopher; Cheng, Zhengdong; Sethuraman, Srinivasan
- Physical Review E, Vol. 66, Issue 1
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
Radiation damage in polymer films from grazing-incidence X-ray scattering measurements
journal, February 2016
- Vaselabadi, Saeed Ahmadi; Shakarisaz, David; Ruchhoeft, Paul
- Journal of Polymer Science Part B: Polymer Physics, Vol. 54, Issue 11
In Situ Characterization of the Self-Assembly of a Polystyrene–Polydimethylsiloxane Block Copolymer during Solvent Vapor Annealing
journal, November 2015
- Bai, W.; Yager, K. G.; Ross, C. A.
- Macromolecules, Vol. 48, Issue 23
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
Fabrication of Nanoporous Alumina Ultrafiltration Membrane with Tunable Pore Size Using Block Copolymer Templates
journal, July 2017
- Zhou, Chun; Segal-Peretz, Tamar; Oruc, Muhammed Enes
- Advanced Functional Materials, Vol. 27, Issue 34
Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains
journal, December 2008
- Han, Eungnak; Stuen, Karl O.; La, Young-Hye
- Macromolecules, Vol. 41, Issue 23
Molecular Transfer Printing Using Block Copolymers
journal, December 2009
- Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang
- ACS Nano, Vol. 4, Issue 2
Arbitrary lattice symmetries via block copolymer nanomeshes
journal, June 2015
- Majewski, Pawel W.; Rahman, Atikur; Black, Charles T.
- Nature Communications, Vol. 6, Issue 1
Ordering Pathway of Block Copolymers under Dynamic Thermal Gradients Studied by in Situ GISAXS
journal, October 2016
- Samant, Saumil; Strzalka, Joseph; Yager, Kevin G.
- Macromolecules, Vol. 49, Issue 22
Molecular weight and polydispersity effects at polymer-polymer interfaces
journal, January 1990
- Broseta, Daniel; Fredrickson, Glenn H.; Helfand, Eugene
- Macromolecules, Vol. 23, Issue 1
Thickness-dependence of block copolymer coarsening kinetics
journal, January 2017
- Black, Charles T.; Forrey, Christopher; Yager, Kevin G.
- Soft Matter, Vol. 13, Issue 18
GISAXS Analysis of the In-Depth Morphology of Thick PS- b -PMMA Films
journal, March 2017
- Ferrarese Lupi, Federico; Giammaria, Tommaso Jacopo; Seguini, Gabriele
- ACS Applied Materials & Interfaces, Vol. 9, Issue 12
High Aspect Ratio PS- b -PMMA Block Copolymer Masks for Lithographic Applications
journal, November 2014
- Ferrarese Lupi, F.; Giammaria, T. J.; Volpe, F. G.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 23
Scherrer grain-size analysis adapted to grazing-incidence scattering with area detectors
journal, October 2009
- Smilgies, Detlef-M.
- Journal of Applied Crystallography, Vol. 42, Issue 6
Micrometer-Scale Ordering of Silicon-Containing Block Copolymer Thin Films via High-Temperature Thermal Treatments
journal, April 2016
- Giammaria, Tommaso Jacopo; Ferrarese Lupi, Federico; Seguini, Gabriele
- ACS Applied Materials & Interfaces, Vol. 8, Issue 15
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
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
Works referencing / citing this record:
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
Nanoscale Block Copolymer Self‐Assembly and Microscale Polymer Film Dewetting: Progress in Understanding the Role of Interfacial Energies in the Formation of Hierarchical Nanostructures
journal, December 2019
- Brassat, Katharina; Lindner, Jörg K. N.
- Advanced Materials Interfaces, Vol. 7, Issue 5
Photothermally Directed Assembly of Block Copolymers
journal, December 2019
- Nowak, Samantha R.; Yager, Kevin G.
- Advanced Materials Interfaces, Vol. 7, Issue 5
Advances in Kriging-Based Autonomous X-Ray Scattering Experiments
journal, January 2020
- Noack, Marcus M.; Doerk, Gregory S.; Li, Ruipeng
- Scientific Reports, Vol. 10, Issue 1