High-throughput morphology mapping of self-assembling ternary polymer blends
Abstract
Multicomponent blending is a convenient yet powerful approach to rationally control the material structure, morphology, and functional properties in solution-deposited films of block copolymers and other self-assembling nanomaterials. However, progress in understanding the structural and morphological dependencies on blend composition is hampered by the time and labor required to synthesize and characterize a large number of discrete samples. Here, we report a new method to systematically explore a wide composition space in ternary blends. Specifically, the blend composition space is divided into gradient segments deposited sequentially on a single wafer by a new gradient electrospray deposition tool, and characterized using high-throughput grazing-incidence small-angle X-ray scattering. This method is applied to the creation of a ternary morphology diagram for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer blended with PS and PMMA homopolymers. Using “wet brush” homopolymers of very low molecular weight (~1 kg mol–1), we identify well-demarcated composition regions comprising highly ordered cylinder, lamellae, and sphere morphologies, as well as a disordered phase at high homopolymer mass fractions. The exquisite granularity afforded by this approach also helps to uncover systematic dependencies among self-assembled morphology, topological grain size, and domain period as functions of homopolymer mass fraction and PS : PMMA ratio.more »
- Authors:
-
- Yale Univ., New Haven, CT (United States)
- Univ. of Pennsylvania, Philadelphia, PA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1749898
- Report Number(s):
- BNL-220736-2020-JAAM
Journal ID: ISSN 2046-2069
- Grant/Contract Number:
- SC0012704; DGE-1122492; CBET-1703494; DMR-1410568
- Resource Type:
- Accepted Manuscript
- Journal Name:
- RSC Advances
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 69; Journal ID: ISSN 2046-2069
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY
Citation Formats
Toth, Kristof, Osuji, Chinedum O., Yager, Kevin G., and Doerk, Gregory S.. High-throughput morphology mapping of self-assembling ternary polymer blends. United States: N. p., 2020.
Web. doi:10.1039/d0ra08491c.
Toth, Kristof, Osuji, Chinedum O., Yager, Kevin G., & Doerk, Gregory S.. High-throughput morphology mapping of self-assembling ternary polymer blends. United States. https://doi.org/10.1039/d0ra08491c
Toth, Kristof, Osuji, Chinedum O., Yager, Kevin G., and Doerk, Gregory S.. Tue .
"High-throughput morphology mapping of self-assembling ternary polymer blends". United States. https://doi.org/10.1039/d0ra08491c. https://www.osti.gov/servlets/purl/1749898.
@article{osti_1749898,
title = {High-throughput morphology mapping of self-assembling ternary polymer blends},
author = {Toth, Kristof and Osuji, Chinedum O. and Yager, Kevin G. and Doerk, Gregory S.},
abstractNote = {Multicomponent blending is a convenient yet powerful approach to rationally control the material structure, morphology, and functional properties in solution-deposited films of block copolymers and other self-assembling nanomaterials. However, progress in understanding the structural and morphological dependencies on blend composition is hampered by the time and labor required to synthesize and characterize a large number of discrete samples. Here, we report a new method to systematically explore a wide composition space in ternary blends. Specifically, the blend composition space is divided into gradient segments deposited sequentially on a single wafer by a new gradient electrospray deposition tool, and characterized using high-throughput grazing-incidence small-angle X-ray scattering. This method is applied to the creation of a ternary morphology diagram for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer blended with PS and PMMA homopolymers. Using “wet brush” homopolymers of very low molecular weight (~1 kg mol–1), we identify well-demarcated composition regions comprising highly ordered cylinder, lamellae, and sphere morphologies, as well as a disordered phase at high homopolymer mass fractions. The exquisite granularity afforded by this approach also helps to uncover systematic dependencies among self-assembled morphology, topological grain size, and domain period as functions of homopolymer mass fraction and PS : PMMA ratio. These results highlight the significant advantages afforded by blending low molecular weight homopolymers for block copolymer self-assembly. Meanwhile, the high-throughput, combinatorial approach to investigating nanomaterial blends introduced here dramatically reduces the time required to explore complex process parameter spaces and is a natural complement to recent advances in autonomous X-ray characterization.},
doi = {10.1039/d0ra08491c},
journal = {RSC Advances},
number = 69,
volume = 10,
place = {United States},
year = {2020},
month = {11}
}
Works referenced in this record:
Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990
- Bates, Frank S.; Fredrickson, Glenn H.
- Annual Review of Physical Chemistry, Vol. 41, Issue 1
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
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
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
Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat
journal, March 2017
- Suh, Hyo Seon; Kim, Do Han; Moni, Priya
- Nature Nanotechnology, Vol. 12, Issue 6
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
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
Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly
journal, November 2014
- Feng, Xunda; Tousley, Marissa E.; Cowan, Matthew G.
- ACS Nano, Vol. 8, Issue 12
Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes
journal, February 2010
- Phillip, William A.; O’Neill, Brandon; Rodwogin, Marc
- ACS Applied Materials & Interfaces, Vol. 2, Issue 3
Highly tunable refractive index visible-light metasurface from block copolymer self-assembly
journal, September 2016
- Kim, Ju Young; Kim, Hyowook; Kim, Bong Hoon
- Nature Communications, Vol. 7, 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
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
Beyond native block copolymer morphologies
journal, January 2017
- Doerk, Gregory S.; Yager, Kevin G.
- Molecular Systems Design & Engineering, Vol. 2, Issue 5
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
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
Gyroid Structures and Morphological Control in Binary Blends of Polystyrene- block -polyisoprene Diblock Copolymers
journal, January 1998
- Sakurai, Shinichi; Irie, Hiroshi; Umeda, Hideo
- Macromolecules, Vol. 31, Issue 2
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
Orientation Control of Block Copolymers Using Surface Active, Phase-Preferential Additives
journal, October 2016
- Vora, Ankit; Schmidt, Kristin; Alva, Gabriela
- ACS Applied Materials & Interfaces, Vol. 8, Issue 43
Orientation Control in Thin Films of a High-χ Block Copolymer with a Surface Active Embedded Neutral Layer
journal, December 2015
- Zhang, Jieqian; Clark, Michael B.; Wu, Chunyi
- Nano Letters, Vol. 16, Issue 1
Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly
journal, January 2020
- Doerk, Gregory S.; Li, Ruipeng; Fukuto, Masafumi
- Macromolecules, Vol. 53, Issue 3
Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends
journal, December 2018
- Doerk, Gregory S.; Li, Ruipeng; Fukuto, Masafumi
- Macromolecules, Vol. 51, Issue 24
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
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
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
Creating Aligned Nanopores by Magnetic Field Processing of Block Copolymer/Homopolymer Blends
journal, February 2019
- Rokhlenko, Yekaterina; Moschovas, Dimitrios; Miskaki, Christina
- ACS Macro Letters, Vol. 8, Issue 3
Nanoporous Block Copolymer Membranes for Ultrafiltration: A Simple Approach to Size Tunability
journal, November 2014
- Ahn, Hyungju; Park, Sungmin; Kim, Sang-Woo
- ACS Nano, Vol. 8, Issue 11
Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995
- Matsen, M. W.
- Macromolecules, Vol. 28, Issue 17
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
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
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
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
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
Phase Behavior of Mixtures of Block Copolymer and Homopolymers in Thin Films and Bulk
journal, May 2003
- Jeong, Unyong; Ryu, Du Yeol; Kho, Dong Han
- Macromolecules, Vol. 36, Issue 10
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
Ordered morphologies in binary blends of diblock copolymer and homopolymer and characterization of their intermaterial dividing surfaces
journal, December 1991
- Winey, Karen I.; Thomas, Edwin L.; Fetters, Lewis J.
- The Journal of Chemical Physics, Vol. 95, Issue 12
Ternary Polymer Blends as Model Surfactant Systems
journal, August 2000
- Washburn, Newell R.; Lodge, Timothy P.; Bates, Frank S.
- The Journal of Physical Chemistry B, Vol. 104, Issue 30
Phase Behavior of Diblock Copolymer–Homopolymer Ternary Blends: Congruent First-Order Lamellar–Disorder Transition
journal, October 2016
- Hickey, Robert J.; Gillard, Timothy M.; Irwin, Matthew T.
- Macromolecules, Vol. 49, Issue 20
Hydrogen bonding strength effect on self-assembly supramolecular structures of diblock copolymer/homopolymer blends
journal, January 2016
- Tsai, Shih-Chi; Lin, Yung-Chih; Lin, En-Li
- Polymer Chemistry, Vol. 7, Issue 13
Morphology Diagram of a Diblock Copolymer−Aluminosilicate Nanoparticle System
journal, November 2009
- Garcia, Benjamin C.; Kamperman, Marleen; Ulrich, Ralph
- Chemistry of Materials, Vol. 21, Issue 22
Phase Behavior of Ternary Homopolymer/Diblock Blends: Influence of Relative Chain Lengths
journal, January 1997
- Janert, Philipp K.; Schick, M.
- Macromolecules, Vol. 30, Issue 1
Hierarchical Porous Polymer Scaffolds from Block Copolymers
journal, August 2013
- Sai, H.; Tan, K. W.; Hur, K.
- Science, Vol. 341, Issue 6145
Emergence of a C15 Laves Phase in Diblock Polymer/Homopolymer Blends
journal, March 2020
- Mueller, Andreas J.; Lindsay, Aaron P.; Jayaraman, Ashish
- ACS Macro Letters, Vol. 9, Issue 4
A15, σ, and a Quasicrystal: Access to Complex Particle Packings via Bidisperse Diblock Copolymer Blends
journal, January 2020
- Lindsay, Aaron P.; Lewis, Ronald M.; Lee, Bongjoon
- ACS Macro Letters, Vol. 9, Issue 2
Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions
journal, February 2020
- Matsushita, Yushu; Takano, Atsushi; Vayer, Marylène
- Advanced Materials Interfaces, Vol. 7, Issue 5
Formation of Tetragonally-Packed Rectangular Cylinders from ABC Block Terpolymer Blends
journal, January 2014
- Asai, Yusuke; Yamada, Kotaro; Yamada, Mutsuhiko
- ACS Macro Letters, Vol. 3, Issue 2
Ordered structure in mixtures of a block copolymer and homopolymers. 2. Effects of molecular weights of homopolymers
journal, October 1990
- Hashimoto, Takeji; Tanaka, Hideaki; Hasegawa, Hirokazu
- Macromolecules, Vol. 23, Issue 20
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
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
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
Pathway-engineering for highly-aligned block copolymer arrays
journal, January 2018
- Choo, Youngwoo; Majewski, Paweł W.; Fukuto, Masafumi
- Nanoscale, Vol. 10, Issue 1
Self-assembly of block copolymer thin films
journal, June 2010
- Albert, Julie N. L.; Epps, Thomas H.
- Materials Today, Vol. 13, Issue 6, p. 24-33
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
Wetting−Dewetting Transition Line in Thin Polymer Films
journal, October 2005
- Ashley, K. M.; Raghavan, D.; Douglas, J. F.
- Langmuir, Vol. 21, Issue 21
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
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 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
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
The role of polydispersity in the lamellar mesophase of model diblock copolymers
journal, December 2007
- Lynd, Nathaniel A.; Hamilton, Benjamin D.; Hillmyer, Marc A.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 45, Issue 24
Lamellar microdomain orientation and phase transition of polystyrene-b-poly(methyl methacrylate) films by controlled interfacial interactions
journal, January 2012
- Choi, Seunghoon; Kim, Eunhye; Ahn, Hyungju
- Soft Matter, Vol. 8, Issue 12
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
In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures
journal, March 2018
- Berezkin, Anatoly V.; Jung, Florian; Posselt, Dorthe
- Advanced Functional Materials, Vol. 28, Issue 19
Ordered Network Mesostructures in Block Polymer Materials
journal, October 2009
- Meuler, Adam J.; Hillmyer, Marc A.; Bates, Frank S.
- Macromolecules, Vol. 42, Issue 19
Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An in Situ GISAXS Study
journal, May 2010
- Paik, Marvin Y.; Bosworth, Joan K.; Smilges, Detlef-M.
- Macromolecules, Vol. 43, Issue 9
Second‐Order Transition Temperatures and Related Properties of Polystyrene. I. Influence of Molecular Weight
journal, June 1950
- Fox, Thomas G.; Flory, Paul J.
- Journal of Applied Physics, Vol. 21, Issue 6
Matrix effects on the diffusion of long polymer chains
journal, July 1986
- Green, Peter F.; Kramer, Edward J.
- Macromolecules, Vol. 19, Issue 4
Polymer diffusion in melt blends of low and high molecular weight
journal, September 1988
- Tead, Stanley F.; Kramer, Edward J.
- Macromolecules, Vol. 21, Issue 5
Diffusion of block copolymers
journal, October 2006
- Yokoyama, Hideaki
- Materials Science and Engineering: R: Reports, Vol. 53, Issue 5-6
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
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
Glass transition of polystyrene versus molecular weight
journal, January 1983
- Claudy, P.; L�toff�, J. M.; Camberlain, Y.
- Polymer Bulletin, Vol. 9-9, Issue 4-5
Interdiffusion and marker movements in concentrated polymer-polymer diffusion couples
journal, April 1984
- Kramer, Edward J.; Green, Peter; Palmstrøm, Christopher J.
- Polymer, Vol. 25, Issue 4
Isotope Effects on Interdiffusion in Blends of Normal and Deuterated Polymers
journal, November 1986
- Green, P. F.; Doyle, B. L.
- Physical Review Letters, Vol. 57, Issue 19
Single-junction polymer solar cells with high efficiency and photovoltage
journal, February 2015
- He, Zhicai; Xiao, Biao; Liu, Feng
- Nature Photonics, Vol. 9, Issue 3
High-performance ternary blend polymer solar cells involving both energy transfer and hole relay processes
journal, June 2015
- Lu, Luyao; Chen, Wei; Xu, Tao
- Nature Communications, Vol. 6, Issue 1
Reducing the efficiency–stability–cost gap of organic photovoltaics with highly efficient and stable small molecule acceptor ternary solar cells
journal, November 2016
- Baran, Derya; Ashraf, Raja Shahid; Hanifi, David A.
- Nature Materials, Vol. 16, Issue 3
High-efficiency colloidal quantum dot infrared light-emitting diodes via engineering at the supra-nanocrystalline level
journal, December 2018
- Pradhan, Santanu; Di Stasio, Francesco; Bi, Yu
- Nature Nanotechnology, Vol. 14, Issue 1
Highly efficient quantum dot near-infrared light-emitting diodes
journal, February 2016
- Gong, Xiwen; Yang, Zhenyu; Walters, Grant
- Nature Photonics, Vol. 10, Issue 4
Enhanced ethylene separation and plasticization resistance in polymer membranes incorporating metal–organic framework nanocrystals
journal, April 2016
- Bachman, Jonathan E.; Smith, Zachary P.; Li, Tao
- Nature Materials, Vol. 15, Issue 8
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