Priming self-assembly pathways by stacking block copolymers

Russell, Sebastian T.; Bae, Suwon; Subramanian, Ashwanth; Tiwale, Nikhil; Doerk, Gregory; Nam, Chang-Yong; Fukuto, Masafumi; Yager, Kevin G.

doi:10.1038/s41467-022-34729-0

Title: Priming self-assembly pathways by stacking block copolymers

Journal Article · Mon Nov 14 00:00:00 EST 2022 · Nature Communications

DOI:https://doi.org/10.1038/s41467-022-34729-0· OSTI ID:1898231

;

; Subramanian, Ashwanth;

;

; Fukuto, Masafumi;

Abstract Block copolymers spontaneously self-assemble into well-defined nanoscale morphologies. Yet equilibrium assembly gives rise to a limited set of structures. Non-equilibrium strategies can, in principle, expand diversity by exploiting self-assembly’s responsive nature. In this vein, we developed a pathway priming strategy combining control of thin film initial configurations and ordering history. We sequentially coat distinct materials to form prescribed initial states, and use thermal annealing to evolve these manifestly non-equilibrium states through the assembly landscape, traversing normally inaccessible transient structures. We explore the enormous associated hyperspace, spanning processing (annealing temperature and time), material (composition and molecular weight), and layering (thickness and order) dimensions. We demonstrate a library of exotic non-native morphologies, including vertically-oriented perforated lamellae, aqueduct structures (vertical lamellar walls with substrate-pinned perforations), parapets (crenellated lamellae), and networks of crisscrossing lamellae. This enhanced structural control can be used to modify functional properties, including accessing regimes that surpass their equilibrium analogs.

View Journal Article

Cite

Export

Save

Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1898231

Alternate ID(s):: OSTI ID: 1922718

Report Number(s):: BNL-223933-2023-JAAM; 6947; PII: 34729

Journal Information:: Nature Communications, Journal Name: Nature Communications Vol. 13 Journal Issue: 1; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

References (64)

Double-slit photoelectron interference in strong-field ionization of the neon dimer Kunitski, Maksim; Eicke, Nicolas; Huber, Pia Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-07882-8	journal	January 2019
Antifogging abilities of model nanotextures Mouterde, Timothée; Lehoucq, Gaëlle; Xavier, Stéphane Nature Materials, Vol. 16, Issue 6 https://doi.org/10.1038/nmat4868	journal	February 2017
Slip Length Enhancement in Nanofluidic Flow using Nanotextured Superhydrophobic Surfaces Heverhagen, Jonas; Tasinkevych, Mykola; Rahman, Atikur Advanced Materials Interfaces, Vol. 3, Issue 17 https://doi.org/10.1002/admi.201600303	journal	June 2016
Templating Three-Dimensional Self-Assembled Structures in Bilayer Block Copolymer Films Tavakkoli K. G., A.; Gotrik, K. W.; Hannon, A. F. Science, Vol. 336, Issue 6086 https://doi.org/10.1126/science.1218437	journal	June 2012
Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates Han, Eungnak; Kang, Huiman; Liu, Chi-Chun Advanced Materials, Vol. 22, Issue 38 https://doi.org/10.1002/adma.201001669	journal	August 2010
Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation Toth, Kristof; Bae, Suwon; Osuji, Chinedum O. Macromolecules, Vol. 54, Issue 17 https://doi.org/10.1021/acs.macromol.1c01032	journal	August 2021
Stimulated Transitions of Directed Nonequilibrium Self-Assemblies Steinschulte, Alexander A.; Scotti, Andrea; Rahimi, Khosrow Advanced Materials, Vol. 29, Issue 43 https://doi.org/10.1002/adma.201703495	journal	October 2017
Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly Feng, Xunda; Tousley, Marissa E.; Cowan, Matthew G. ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505037b	journal	November 2014
Emergent Hybrid Nanostructures Based on Non-Equilibrium Block Copolymer Self-Assembly Li, Mei; Mann, Stephen Angewandte Chemie International Edition, Vol. 47, Issue 49 https://doi.org/10.1002/anie.200803231	journal	November 2008
Sub-10 nm Nanofabrication via Nanoimprint Directed Self-Assembly of Block Copolymers Park, Sang-Min; Liang, Xiaogan; Harteneck, Bruce D. ACS Nano, Vol. 5, Issue 11 https://doi.org/10.1021/nn201391d	journal	October 2011
Pathway-engineering for highly-aligned block copolymer arrays Choo, Youngwoo; Majewski, Paweł W.; Fukuto, Masafumi Nanoscale, Vol. 10, Issue 1 https://doi.org/10.1039/C7NR06069F	journal	January 2018
Controlling Polymer-Surface Interactions with Random Copolymer Brushes Mansky, P.; Liu, Y.; Huang, E. Science, Vol. 275, Issue 5305, p. 1458-1460 https://doi.org/10.1126/science.275.5305.1458	journal	March 1997
Life as a Nanoscale Phenomenon Mann, Stephen Angewandte Chemie International Edition, Vol. 47, Issue 29 https://doi.org/10.1002/anie.200705538	journal	July 2008
Effect of Humidity on the Ordering of PEO-Based Copolymer Thin Films Bang, Joona; Kim, Bumjoon J.; Stein, Gila E. Macromolecules, Vol. 40, Issue 19 https://doi.org/10.1021/ma0710737	journal	September 2007
Fast Parallel Algorithms for Short-Range Molecular Dynamics Plimpton, Steve Journal of Computational Physics, Vol. 117, Issue 1 https://doi.org/10.1006/jcph.1995.1039	journal	March 1995
Self-assembly of block copolymer thin films Albert, Julie N. L.; Epps, Thomas H. Materials Today, Vol. 13, Issue 6, p. 24-33 https://doi.org/10.1016/S1369-7021(10)70106-1	journal	June 2010
Rapid ordering of block copolymer thin films Majewski, Pawel W.; Yager, Kevin G. Journal of Physics: Condensed Matter, Vol. 28, Issue 40 https://doi.org/10.1088/0953-8984/28/40/403002	journal	August 2016
Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields Morkved, T. L.; Lu, M.; Urbas, A. M. Science, Vol. 273, Issue 5277 https://doi.org/10.1126/science.273.5277.931	journal	August 1996
Patterning with block copolymer thin films Segalman, Rachel A. Materials Science and Engineering: R: Reports, Vol. 48, Issue 6, p. 191-226 https://doi.org/10.1016/j.mser.2004.12.003	journal	February 2005
Nanodomain control in copolymer thin films Huang, E.; Rockford, L.; Russell, T. P. Nature, Vol. 395, Issue 6704 https://doi.org/10.1038/27358	journal	October 1998
Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films Majewski, Pawel W.; Yager, Kevin G. Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b01463	journal	July 2015
Block Copolymer Thin Films: Physics and Applications Fasolka, Michael J.; Mayes, Anne M. Annual Review of Materials Research, Vol. 31, Issue 1, p. 323-355 https://doi.org/10.1146/annurev.matsci.31.1.323	journal	August 2001
Block Copolymer Thermodynamics: Theory and Experiment Bates, Frank S.; Fredrickson, Glenn H. Annual Review of Physical Chemistry, Vol. 41, Issue 1 https://doi.org/10.1146/annurev.pc.41.100190.002521	journal	October 1990
Epitaxial Transitions among FCC, HCP, BCC, and Cylinder Phases in a Block Copolymer Solution Park, Moon Jeong; Bang, Joona; Harada, Tamotsu Macromolecules, Vol. 37, Issue 24 https://doi.org/10.1021/ma049285g	journal	November 2004
Orientational Preference in Multilayer Block Copolymer Nanomeshes with Respect to Layer-to-Layer Commensurability Carpenter, Corinne L.; Nicaise, Samuel; Theofanis, Patrick Lauren Macromolecules, Vol. 50, Issue 20 https://doi.org/10.1021/acs.macromol.7b01290	journal	October 2017
Micro- and nanotechnology via reaction–diffusion Grzybowski, Bartosz A.; Bishop, Kyle J. M.; Campbell, Christopher J. Soft Matter, Vol. 1, Issue 2 https://doi.org/10.1039/b501769f	journal	January 2005
Translational Dynamics of Diblock Copolymers Green, Peter F. Macromolecules, Vol. 28, Issue 7 https://doi.org/10.1021/ma00111a008	journal	March 1995
Flexible and Transferrable Self-Assembled Nanopatterning on Chemically Modified Graphene Kim, Ju Young; Kim, Bong Hoon; Hwang, Jin Ok Advanced Materials, Vol. 25, Issue 9 https://doi.org/10.1002/adma.201204131	journal	December 2012
Dynamics of entangled linear polymer melts: A molecular‐dynamics simulation Kremer, Kurt; Grest, Gary S. The Journal of Chemical Physics, Vol. 92, Issue 8 https://doi.org/10.1063/1.458541	journal	April 1990
Dissipative adaptation in driven self-assembly leading to self-dividing fibrils te Brinke, Esra; Groen, Joost; Herrmann, Andreas Nature Nanotechnology, Vol. 13, Issue 9 https://doi.org/10.1038/s41565-018-0192-1	journal	July 2018
Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films Subramanian, Ashwanth; Doerk, Gregory; Kisslinger, Kim Nanoscale, Vol. 11, Issue 19 https://doi.org/10.1039/C9NR00206E	journal	January 2019
Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions Han, Eungnak; Stuen, Karl O.; Leolukman, Melvina Macromolecules, Vol. 42, Issue 13 https://doi.org/10.1021/ma9002903	journal	July 2009
Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement Diederichsen, Kyle M.; Brow, Ryan R.; Stoykovich, Mark P. ACS Nano, Vol. 9, Issue 3 https://doi.org/10.1021/acsnano.5b01321	journal	February 2015
Tough, Bio-Inspired Hybrid Materials Munch, E.; Launey, M. E.; Alsem, D. H. Science, Vol. 322, Issue 5907 https://doi.org/10.1126/science.1164865	journal	December 2008
Nanostructure engineering by templated self-assembly of block copolymers Cheng, Joy Y.; Mayes, Anne M.; Ross, Caroline A. Nature Materials, Vol. 3, Issue 11 https://doi.org/10.1038/nmat1211	journal	October 2004
Photothermally Directed Assembly of Block Copolymers Nowak, Samantha R.; Yager, Kevin G. Advanced Materials Interfaces, Vol. 7, Issue 5 https://doi.org/10.1002/admi.201901679	journal	December 2019
Beyond native block copolymer morphologies Doerk, Gregory S.; Yager, Kevin G. Molecular Systems Design & Engineering, Vol. 2, Issue 5 https://doi.org/10.1039/C7ME00069C	journal	January 2017
Anisotropic Ionic Conductivity in Block Copolymer Membranes by Magnetic Field Alignment Majewski, Pawel W.; Gopinadhan, Manesh; Jang, Woo-Sik Journal of the American Chemical Society, Vol. 132, Issue 49 https://doi.org/10.1021/ja107309p	journal	December 2010
Entropic segregation of short polymers to the surface of a polydisperse melt Mahmoudi, P.; Matsen, M. W. The European Physical Journal E, Vol. 40, Issue 10 https://doi.org/10.1140/epje/i2017-11575-7	journal	October 2017
Block Copolymer Response to Photothermal Stress Fields Majewski, Pawel W.; Yager, Kevin G. Macromolecules, Vol. 48, Issue 13 https://doi.org/10.1021/acs.macromol.5b00955	journal	June 2015
Non-native three-dimensional block copolymer morphologies Rahman, Atikur; Majewski, Pawel W.; Doerk, Gregory Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13988	journal	December 2016
Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns Bang, Joona; Jeong, Unyong; Ryu, Du Yeol Advanced Materials, Vol. 21, Issue 47, p. 4769-4792 https://doi.org/10.1002/adma.200803302	journal	July 2009
Dynamics of pattern coarsening in a two-dimensional smectic system Harrison, Christopher; Cheng, Zhengdong; Sethuraman, Srinivasan Physical Review E, Vol. 66, Issue 1 https://doi.org/10.1103/PhysRevE.66.011706	journal	July 2002
Three-Dimensional Multilayered Nanostructures from Crosslinkable Block Copolymers Woo, Sanghoon; Wang, Hyun Suk; Choe, Youngson ACS Macro Letters, Vol. 5, Issue 3 https://doi.org/10.1021/acsmacrolett.5b00908	journal	February 2016
Sub-50-nm self-assembled nanotextures for enhanced broadband antireflection in silicon solar cells Rahman, Atikur; Ashraf, Ahsan; Xin, Huolin Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms6963	journal	January 2015
Reaction–diffusion processes at the nano- and microscales Epstein, Irving R.; Xu, Bing Nature Nanotechnology, Vol. 11, Issue 4 https://doi.org/10.1038/nnano.2016.41	journal	April 2016
Multilayer block copolymer meshes by orthogonal self-assembly Tavakkoli K. G., Amir; Nicaise, Samuel M.; Gadelrab, Karim R. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10518	journal	January 2016
Morphologies of block copolymer melts Castelletto, V.; Hamley, I. W. Current Opinion in Solid State and Materials Science, Vol. 8, Issue 6 https://doi.org/10.1016/j.cossms.2005.06.001	journal	December 2004
Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions Mann, Stephen Nature Materials, Vol. 8, Issue 10 https://doi.org/10.1038/nmat2496	journal	September 2009
Three-dimensional mesoporous structures fabricated by independent stacking of self-assembled films on suspended membranes Rose, F.; Bosworth, J. K.; Dobisz, E. A. Nanotechnology, Vol. 22, Issue 3 https://doi.org/10.1088/0957-4484/22/3/035603	journal	December 2010
Large mobility modulation in ultrathin amorphous titanium oxide transistors Tiwale, Nikhil; Subramanian, Ashwanth; Dai, Zhongwei Communications Materials, Vol. 1, Issue 1 https://doi.org/10.1038/s43246-020-00096-w	journal	December 2020
Arbitrary lattice symmetries via block copolymer nanomeshes Majewski, Pawel W.; Rahman, Atikur; Black, Charles T. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8448	journal	June 2015
Ordering Pathway of Block Copolymers under Dynamic Thermal Gradients Studied by in Situ GISAXS Samant, Saumil; Strzalka, Joseph; Yager, Kevin G. Macromolecules, Vol. 49, Issue 22 https://doi.org/10.1021/acs.macromol.6b01555	journal	October 2016
Nanotransfer Printing with sub-10 nm Resolution Realized using Directed Self-Assembly Jeong, Jae Won; Park, Woon Ik; Do, Lee-Mi Advanced Materials, Vol. 24, Issue 26 https://doi.org/10.1002/adma.201200356	journal	June 2012
Photoswitchable Phase Separation and Oligonucleotide Trafficking in DNA Coacervate Microdroplets Martin, Nicolas; Tian, Liangfei; Spencer, Dan Angewandte Chemie International Edition, Vol. 58, Issue 41 https://doi.org/10.1002/anie.201909228	journal	September 2019
Matplotlib: A 2D Graphics Environment Hunter, John D. Computing in Science & Engineering, Vol. 9, Issue 3 https://doi.org/10.1109/MCSE.2007.55	journal	January 2007
Controlling Domain Spacing and Grain Size in Cylindrical Block Copolymer Thin Films by Means of Thermal and Solvent Vapor Annealing Gu, Xiaodan; Gunkel, Ilja; Hexemer, Alexander Macromolecules, Vol. 49, Issue 9 https://doi.org/10.1021/acs.macromol.6b00429	journal	April 2016
Python for Scientific Computing Oliphant, Travis E. Computing in Science & Engineering, Vol. 9, Issue 3 https://doi.org/10.1109/MCSE.2007.58	journal	January 2007
Molecular Dynamics Study of the Role of the Free Surface on Block Copolymer Thin Film Morphology and Alignment Forrey, Christopher; Yager, Kevin G.; Broadaway, Samuel P. ACS Nano, Vol. 5, Issue 4 https://doi.org/10.1021/nn103502p	journal	March 2011
Overcoming Interfacial Interactions with Electric Fields Thurn-Albrecht, T.; DeRouchey, J.; Russell, T. P. Macromolecules, Vol. 33, Issue 9, p. 3250-3253 https://doi.org/10.1021/ma991896z	journal	May 2000
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Tunable and rapid self-assembly of block copolymers using mixed solvent vapors Park, Woon Ik; Tong, Sheng; Liu, Yuzi Nanoscale, Vol. 6, Issue 24 https://doi.org/10.1039/C4NR04726E	journal	January 2014
Robust Superhydrophobicity in Large-Area Nanostructured Surfaces Defined by Block-Copolymer Self Assembly Checco, Antonio; Rahman, Atikur; Black, Charles T. Advanced Materials, Vol. 26, Issue 6 https://doi.org/10.1002/adma.201304006	journal	October 2013
Role of Defects in Ion Transport in Block Copolymer Electrolytes Kambe, Yu; Arges, Christopher G.; Czaplewski, David A. Nano Letters, Vol. 19, Issue 7 https://doi.org/10.1021/acs.nanolett.9b01758	journal	June 2019

Similar Records

Ultra-Fast Vertical Ordering of Lamellar Block Copolymer Films on Unmodified Substrates

Journal Article · Wed Jan 20 00:00:00 EST 2021 · Macromolecules · OSTI ID:1898231

Singh, Maninderjeet; Wu, Wenjie; Basutkar, Monali N.; +4 more

Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing [Thru-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing]

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Nano Letters · OSTI ID:1898231

Basutkar, Monali N.; Samant, Saumil; Strzalka, Joseph; +3 more

Combinatorial Block Copolymer Ordering on Tunable Rough

Journal Article · Tue May 01 00:00:00 EDT 2012 · Macromolecules · OSTI ID:1898231

M, Kulkarni M; Yager, K; Sharma, A; +1 more

Related Subjects

77 NANOSCIENCE AND NANOTECHNOLOGY
molecular self-assembly
polymers
self-assembly

Title: Priming self-assembly pathways by stacking block copolymers

Citation Formats

References (64)

Similar Records

Related Subjects