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

Singh, Maninderjeet; Wu, Wenjie; Basutkar, Monali N.; Strzalka, Joseph; Al-Enizi, Abdullah M.; Douglas, Jack F.; Karim, Alamgir

doi:10.1021/acs.macromol.0c01782

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

Journal Article · Wed Jan 20 00:00:00 EST 2021 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c01782· OSTI ID:1774155

Singh, Maninderjeet ^[1]; Wu, Wenjie ^[1];

^[2];

^[3];

^[4];

^[5];

^[1]

Univ. of Houston, TX (United States)
Univ. of Akron, OH (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
King Saud Univ., Riyadh (Saudi Arabia)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

To utilize the full potential of block copolymer (BCP) thin films for use in technological devices ranging from ion conduction membranes, transistors to nanowire array antennas, rapid self- assembly of lamellar block copolymers (l-BCPs) with vertically oriented lamellar domains on a variety of unmodified substrates is needed. l-BCPs have an inherently larger interfacial area for transport compared to their cylindrical counterpart. Our observations demonstrate that the as-cast weakly ordered vertically oriented state of l-BCP films of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) from directional evaporation of select solvents, act as “seed templates” for their ultra-fast evolution (~30 s) into well-ordered vertically oriented nanostructures, using a thermal gradient-based Cold Zone Annealing (CZA) technique. Furthermore, vertical lamellae are obtained on unmodified substrates, Quartz and Kapton, and the kinetics of l-BCP ordering is much faster by CZA as compared to the isotropic oven annealing. The rapid ordering kinetics of vertical l-BCPs is tested and found applicable to different molecular weights and film thicknesses ranging from 20 nm to 480 nm, which ultimately flip over to their equilibrium parallel morphology at upper limits of annealing times. This rapid ordering strategy for vertical orientation of l-BCPs using roll-to-roll compatible CZA would be highly relevant for fundamental studies of interfacial transport as well as for industrial applications from membranes to nanowires.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF); King Saud University

Grant/Contract Number:: AC02-06CH11357; DMR 1905996

OSTI ID:: 1774155

Journal Information:: Macromolecules, Vol. 54, Issue 3; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (43)

Block Copolymer Lithography Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W. Macromolecules, Vol. 47, Issue 1, p. 2-12 https://doi.org/10.1021/ma401762n	journal	November 2013
Graphoepitaxy of Spherical Domain Block Copolymer Films Segalman, R. A.; Yokoyama, H.; Kramer, E. J. Advanced Materials, Vol. 13, Issue 15, p. 1152-1155 https://doi.org/10.1002/1521-4095(200108)13:15<1152::aid-adma1152>3.0.co;2-5	journal	August 2001
Through-Thickness Vertically Ordered Lamellar Block Copolymer Thin Films on Unmodified Quartz with Cold Zone Annealing Basutkar, Monali N.; Samant, Saumil; Strzalka, Joseph Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b04028	journal	November 2017
Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors Samant, Saumil P.; Grabowski, Christopher A.; Kisslinger, Kim ACS Applied Materials & Interfaces, Vol. 8, Issue 12 https://doi.org/10.1021/acsami.5b11851	journal	March 2016
Induced Orientational Order in Symmetric Diblock Copolymer Thin Films Ruiz, R.; Sandstrom, R. L.; Black, C. T. Advanced Materials, Vol. 19, Issue 4 https://doi.org/10.1002/adma.200600287	journal	February 2007
Strategies for Inorganic Incorporation using Neat Block Copolymer Thin Films for Etch Mask Function and Nanotechnological Application Cummins, Cian; Ghoshal, Tandra; Holmes, Justin D. Advanced Materials, Vol. 28, Issue 27 https://doi.org/10.1002/adma.201503432	journal	January 2016
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
Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter Hu, Hanqiong; Gopinadhan, Manesh; Osuji, Chinedum O. Soft Matter, Vol. 10, Issue 22 https://doi.org/10.1039/c3sm52607k	journal	January 2014
Generating thickness gradients of thin polymer films via flow coating Stafford, Christopher M.; Roskov, Kristen E.; Epps, Thomas H. Review of Scientific Instruments, Vol. 77, Issue 2 https://doi.org/10.1063/1.2173072	journal	February 2006
Solvent Vapor Annealing of Block Polymer Thin Films Sinturel, Christophe; Vayer, Marylène; Morris, Michael Macromolecules, Vol. 46, Issue 14 https://doi.org/10.1021/ma400735a	journal	June 2013
Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates Ouk Kim, Sang; Solak, Harun H.; Stoykovich, Mark P. Nature, Vol. 424, Issue 6947, p. 411-414 https://doi.org/10.1038/nature01775	journal	July 2003
Self-assembly of block copolymers Mai, Yiyong; Eisenberg, Adi Chemical Society Reviews, Vol. 41, Issue 18 https://doi.org/10.1039/c2cs35115c	journal	January 2012
Ordering in thin films of block copolymers: Fundamentals to potential applications Hamley, I. W. Progress in Polymer Science, Vol. 34, Issue 11 https://doi.org/10.1016/j.progpolymsci.2009.06.003	journal	November 2009
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly Ruiz, R.; Kang, H.; Detcheverry, F. A. Science, Vol. 321, Issue 5891 https://doi.org/10.1126/science.1157626	journal	August 2008
Polymer Electrolytes Hallinan, Daniel T.; Balsara, Nitash P. Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-071312-121705	journal	July 2013
Block copolymer electrolytes for rechargeable lithium batteries Young, Wen-Shiue; Kuan, Wei-Fan; Epps, Thomas H. Journal of Polymer Science Part B: Polymer Physics, Vol. 52, Issue 1 https://doi.org/10.1002/polb.23404	journal	November 2013
Ionic Conductivity of Low Molecular Weight Block Copolymer Electrolytes Yuan, Rodger; Teran, Alexander A.; Gurevitch, Inna Macromolecules, Vol. 46, Issue 3 https://doi.org/10.1021/ma3024552	journal	January 2013
Metal-Containing Block Copolymer Thin Films Yield Wire Grid Polarizers with High Aspect Ratio Kim, So Youn; Gwyther, Jessica; Manners, Ian Advanced Materials, Vol. 26, Issue 5 https://doi.org/10.1002/adma.201303452	journal	October 2013
Aligned Morphologies in Near-Edge Regions of Block Copolymer Thin Films Basutkar, Monali N.; Majewski, Pawel W.; Doerk, Gregory S. Macromolecules, Vol. 52, Issue 19 https://doi.org/10.1021/acs.macromol.9b01703	journal	September 2019
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
Orientational Order in Block Copolymer Films Zone Annealed below the Order−Disorder Transition Temperature Berry, Brian C.; Bosse, August W.; Douglas, Jack F. Nano Letters, Vol. 7, Issue 9 https://doi.org/10.1021/nl071354s	journal	September 2007
Fast Assembly of Ordered Block Copolymer Nanostructures through Microwave Annealing Zhang, Xiaojiang; Harris, Kenneth D.; Wu, Nathanael L. Y. ACS Nano, Vol. 4, Issue 11 https://doi.org/10.1021/nn102387c	journal	October 2010
Solvent-Induced Transition from Micelles in Solution to Cylindrical Microdomains in Diblock Copolymer Thin Films Park, Soojin; Wang, Jia-Yu; Kim, Bokyung Macromolecules, Vol. 40, Issue 25, p. 9059-9063 https://doi.org/10.1021/ma071321z	journal	December 2007
Understanding Film Formation Morphology and Orientation in High Member 2D Ruddlesden-Popper Perovskites for High-Efficiency Solar Cells Soe, Chan Myae Myae; Nie, Wanyi; Stoumpos, Constantinos C. Advanced Energy Materials, Vol. 8, Issue 1 https://doi.org/10.1002/aenm.201700979	journal	September 2017
Block copolymer/ionic liquid films: The effect of ionic liquid composition on morphology and ion conduction Gwee, Liang; Choi, Jae-Hong; Winey, Karen I. Polymer, Vol. 51, Issue 23 https://doi.org/10.1016/j.polymer.2010.09.026	journal	October 2010
Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films Singh, Gurpreet; Yager, Kevin G.; Berry, Brian ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn304266f	journal	October 2012
Effect of Molecular Weight and Layer Thickness on the Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films Samant, Saumil; Basutkar, Monali; Singh, Maninderjeet ACS Applied Polymer Materials, Vol. 2, Issue 8 https://doi.org/10.1021/acsapm.0c00127	journal	June 2020
Direct Immersion Annealing of Thin Block Copolymer Films Modi, Arvind; Bhaway, Sarang M.; Vogt, Bryan D. ACS Applied Materials & Interfaces, Vol. 7, Issue 39 https://doi.org/10.1021/acsami.5b06259	journal	September 2015
GIXSGUI : a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films Jiang, Zhang Journal of Applied Crystallography, Vol. 48, Issue 3 https://doi.org/10.1107/s1600576715004434	journal	April 2015
Tuning Molecular Relaxation for Vertical Orientation in Cylindrical Block Copolymer Films via Sharp Dynamic Zone Annealing Singh, Gurpreet; Yager, Kevin G.; Smilgies, Detlef-M. Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma301004j	journal	August 2012
Millisecond Ordering of Block Copolymer Films via Photothermal Gradients Majewski, Pawel W.; Yager, Kevin G. ACS Nano, Vol. 9, Issue 4 https://doi.org/10.1021/nn5071827	journal	February 2015
Block copolymers for supercapacitors, dielectric capacitors and batteries Liu, Tianyu; Liu, Guoliang Journal of Physics: Condensed Matter, Vol. 31, Issue 23 https://doi.org/10.1088/1361-648x/ab0d77	journal	March 2019
Device-Scale Perpendicular Alignment of Colloidal Nanorods Baker, Jessy L.; Widmer-Cooper, Asaph; Toney, Michael F. Nano Letters, Vol. 10, Issue 1 https://doi.org/10.1021/nl903187v	journal	January 2010
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
Rapid thermal processing of self-assembling block copolymer thin films Ferrarese Lupi, F.; Giammaria, T. J.; Ceresoli, M. Nanotechnology, Vol. 24, Issue 31 https://doi.org/10.1088/0957-4484/24/31/315601	journal	July 2013
Surface Morphology Diagram for Cylinder-Forming Block Copolymer Thin Films Zhang, Xiaohua; Berry, Brian C.; Yager, Kevin G. ACS Nano, Vol. 2, Issue 11 https://doi.org/10.1021/nn800643x	journal	November 2008
Block copolymers: controlling nanostructure to generate functional materials – synthesis, characterization, and engineering Epps, III, Thomas H.; O'Reilly, Rachel K. Chemical Science, Vol. 7, Issue 3 https://doi.org/10.1039/c5sc03505h	journal	January 2016
Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends Doerk, Gregory S.; Li, Ruipeng; Fukuto, Masafumi Macromolecules, Vol. 51, Issue 24 https://doi.org/10.1021/acs.macromol.8b01773	journal	December 2018
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
Block copolymer derived 3-D interpenetrating multifunctional gyroidal nanohybrids for electrical energy storage Werner, J. G.; Rodríguez-Calero, G. G.; Abruña, H. D. Energy & Environmental Science, Vol. 11, Issue 5 https://doi.org/10.1039/c7ee03571c	journal	January 2018
Self-Assembled Block Copolymer Thin Films as Water Filtration Membranes Phillip, William A.; O’Neill, Brandon; Rodwogin, Marc ACS Applied Materials & Interfaces, Vol. 2, Issue 3 https://doi.org/10.1021/am900882t	journal	February 2010
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

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:1774155

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

Interfacial Behavior of Polymers: Using Interfaces to Manipulate Polymers

Technical Report · Thu Feb 26 00:00:00 EST 2015 · OSTI ID:1774155

Russell, Thomas P.

Ordering pathway of block copolymers under dynamic thermal gradients studied by in situ GISAXS

Journal Article · Mon Oct 31 00:00:00 EDT 2016 · Macromolecules · OSTI ID:1774155

Samant, Saumil; Strzalka, Joseph; Yager, Kevin G.; +7 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Flexible substrates
Block copolymers
Gradient annealing
Lamellae
Rapid
Self-assembly
Thin films
Unmodified substrates
Thickness
Morphology
Grain

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

Citation Formats

References (43)

Similar Records

Related Subjects