Templated Self-Assembly of a PS- Branch -PDMS Bottlebrush Copolymer

Cheng, Li-Chen; Gadelrab, Karim R.; Kawamoto, Ken; Yager, Kevin G.; Johnson, Jeremiah A.; Alexander-Katz, Alfredo; Ross, Caroline A.

doi:10.1021/acs.nanolett.8b01389

Templated Self-Assembly of a PS- Branch -PDMS Bottlebrush Copolymer

Journal Article · Thu Jun 07 00:00:00 EDT 2018 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.8b01389· OSTI ID:1469783

^[1]; ^[1]; Kawamoto, Ken ^[1]; ^[2]; ^[1]; Alexander-Katz, Alfredo ^[1]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States)

The self-assembly of block copolymers with novel architectures offers tremendous opportunities in nanoscale patterning and fabrication. Here, the thin film morphology, annealing kinetics, and topographical templating of an unconventional Janus-type “PS-branch-PDMS” bottlebrush copolymer (BBCP) is described. In the Janus-type BBCP, each segment of the backbone connects two immiscible sidechain blocks, instead of having each type of sidechain at one end of the molecule as in a conventional BBCP. Thin films of a Janus-type BBCP with M_n = 609 kg/mol exhibited 22 nm period cylindrical microdomains with long-range order under solvent vapor annealing, and the effects of as-cast film thickness, solvent vapor pressure, and composition of the binary mixture of solvent vapors are described. The dynamic self-assembly process was characterized using in-situ grazing-incidence x-ray scattering. Templated selfassembly of the BBCP within lithographically patterned substrates was demonstrated, showing distinct pattern orientation and dimensions that differ from conventional BCPs. Self-consistent field theory is used to elucidate details of the templated self-assembly behavior within confinement.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1469783

Report Number(s):: BNL--209025-2018-JAAM

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 7 Vol. 18; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (45)

Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation Kim, S. H.; Misner, M. J.; Xu, T. Advanced Materials, Vol. 16, Issue 3, p. 226-231 https://doi.org/10.1002/adma.200304906	journal	February 2004
Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns Jung, Yeon Sik; Ross, Caroline A. Advanced Materials, Vol. 21, Issue 24 https://doi.org/10.1002/adma.200802855	journal	June 2009
An In Situ Grazing Incidence X-Ray Scattering Study of Block Copolymer Thin Films During Solvent Vapor Annealing Gu, Xiaodan; Gunkel, Ilja; Hexemer, Alexander Advanced Materials, Vol. 26, Issue 2 https://doi.org/10.1002/adma.201302562	journal	November 2013
Precisely Tunable Photonic Crystals From Rapidly Self-Assembling Brush Block Copolymer Blends Miyake, Garret M.; Piunova, Victoria A.; Weitekamp, Raymond A. Angewandte Chemie International Edition, Vol. 51, Issue 45, p. 11246-11248 https://doi.org/10.1002/anie.201205743	journal	September 2012
Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties Guo, Zi-Hao; Le, An N.; Feng, Xunda Angewandte Chemie International Edition, Vol. 57, Issue 28 https://doi.org/10.1002/anie.201802844	journal	May 2018
Diblock copolymer thin films: Parallel and perpendicular lamellar phases in the weak segregation limit Tsori, Y.; Andelman, D. The European Physical Journal E, Vol. 5, Issue 5 https://doi.org/10.1007/s101890170044	journal	August 2001
Coexistence curves of polystyrene/ poly(dimethylsiloxane) blends Nose, Takuhei Polymer, Vol. 36, Issue 11 https://doi.org/10.1016/0032-3861(95)95303-I	journal	January 1995
Block copolymers and conventional lithography Stoykovich, Mark P.; Nealey, Paul F. Materials Today, Vol. 9, Issue 9, p. 20-29 https://doi.org/10.1016/S1369-7021(06)71619-4	journal	September 2006
Block copolymer patterns and templates Li, Mingqi; Ober, Christopher K. Materials Today, Vol. 9, Issue 9, p. 30-39 https://doi.org/10.1016/S1369-7021(06)71620-0	journal	September 2006
Cylindrical molecular brushes: Synthesis, characterization, and properties Sheiko, Sergei S.; Sumerlin, Brent S.; Matyjaszewski, Krzysztof Progress in Polymer Science, Vol. 33, Issue 7 https://doi.org/10.1016/j.progpolymsci.2008.05.001	journal	July 2008
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
Combining Graphoepitaxy and Electric Fields toward Uniaxial Alignment of Solvent-Annealed Polystyrene– b –Poly(dimethylsiloxane) Block Copolymers Kathrein, Christine C.; Bai, Wubin; Currivan-Incorvia, Jean Anne Chemistry of Materials, Vol. 27, Issue 19 https://doi.org/10.1021/acs.chemmater.5b03354	journal	September 2015
In Situ Characterization of the Self-Assembly of a Polystyrene–Polydimethylsiloxane Block Copolymer during Solvent Vapor Annealing Bai, W.; Yager, K. G.; Ross, C. A. Macromolecules, Vol. 48, Issue 23 https://doi.org/10.1021/acs.macromol.5b02174	journal	November 2015
Scalable Synthesis of Multivalent Macromonomers for ROMP Nguyen, Hung V. -T.; Gallagher, Nolan M.; Vohidov, Farrukh ACS Macro Letters, Vol. 7, Issue 4 https://doi.org/10.1021/acsmacrolett.8b00201	journal	March 2018
Bottlebrush Block Polymers: Quantitative Theory and Experiments Dalsin, Samuel J.; Rions-Maehren, Thomas G.; Beam, Marissa D. ACS Nano, Vol. 9, Issue 12 https://doi.org/10.1021/acsnano.5b05473	journal	October 2015
Vapor Pressure of Toluene up to the Critical Temperature Krase, Norman W.; Goodman, J. B. Industrial & Engineering Chemistry, Vol. 22, Issue 1 https://doi.org/10.1021/ie50241a004	journal	January 1930
Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement Xia, Yan; Olsen, Bradley D.; Kornfield, Julia A. Journal of the American Chemical Society, Vol. 131, Issue 51, p. 18525-18532 https://doi.org/10.1021/ja908379q	journal	December 2009
Graft-through Synthesis and Assembly of Janus Bottlebrush Polymers from A- Branch -B Diblock Macromonomers Kawamoto, Ken; Zhong, Mingjiang; Gadelrab, Karim R. Journal of the American Chemical Society, Vol. 138, Issue 36 https://doi.org/10.1021/jacs.6b07670	journal	September 2016
Surfactant-induced lyotropic behavior of flexible polymer solutions Fredrickson, Glenn H. Macromolecules, Vol. 26, Issue 11 https://doi.org/10.1021/ma00063a029	journal	May 1993
The Full Phase Behavior for Block Copolymers in Solvents of Varying Selectivity Lodge, Timothy P.; Pudil, Bryant; Hanley, Kenneth J. Macromolecules, Vol. 35, Issue 12 https://doi.org/10.1021/ma0200975	journal	June 2002
Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography Kennemur, Justin G.; Yao, Li; Bates, Frank S. Macromolecules, Vol. 47, Issue 4 https://doi.org/10.1021/ma4020164	journal	February 2014
Thin Film Morphologies of Bulk-Gyroid Polystyrene- block -polydimethylsiloxane under Solvent Vapor Annealing Bai, Wubin; Hannon, Adam F.; Gotrik, Kevin W. Macromolecules, Vol. 47, Issue 17 https://doi.org/10.1021/ma501293n	journal	August 2014
Domain-Boundary Structure of Styrene-Isoprene Block Copolymer Films Cast from Solution. 4. Molecular-Weight Dependence of Lamellar Microdomains Hashimoto, Takeji; Shibayama, Mitsuhiro; Kawai, Hiromichi Macromolecules, Vol. 13, Issue 5 https://doi.org/10.1021/ma60077a040	journal	September 1980
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Synthesis of Polystyrene−Polylactide Bottlebrush Block Copolymers and Their Melt Self-Assembly into Large Domain Nanostructures Rzayev, Javid Macromolecules, Vol. 42, Issue 6 https://doi.org/10.1021/ma802304y	journal	March 2009
Efficient Synthesis of Narrowly Dispersed Brush Polymers via Living Ring-Opening Metathesis Polymerization of Macromonomers Xia, Yan; Kornfield, Julia A.; Grubbs, Robert H. Macromolecules, Vol. 42, Issue 11, p. 3761-3766 https://doi.org/10.1021/ma900280c	journal	June 2009
Structural Rearrangements in a Lamellar Diblock Copolymer Thin Film during Treatment with Saturated Solvent Vapor Di, Zhenyu; Posselt, Dorthe; Smilgies, Detlef-M. Macromolecules, Vol. 43, Issue 1 https://doi.org/10.1021/ma9017795	journal	January 2010
Orientation-Controlled Self-Assembled Nanolithography Using a Polystyrene−Polydimethylsiloxane Block Copolymer Jung, Yeon Sik; Ross, C. A. Nano Letters, Vol. 7, Issue 7 https://doi.org/10.1021/nl070924l	journal	July 2007
Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine- b -dimethylsiloxane) Block Copolymer Jeong, Jae Won; Park, Woon Ik; Kim, Mi-Jeong Nano Letters, Vol. 11, Issue 10 https://doi.org/10.1021/nl2016224	journal	October 2011
Morphology Control in Block Copolymer Films Using Mixed Solvent Vapors Gotrik, Kevin W.; Hannon, Adam F.; Son, Jeong Gon ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn302641z	journal	August 2012
Self-Assembly of Symmetric Brush Diblock Copolymers Gu, Weiyin; Huh, June; Hong, Sung Woo ACS Nano, Vol. 7, Issue 3 https://doi.org/10.1021/nn305867d	journal	February 2013
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
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
Structure, function, self-assembly, and applications of bottlebrush copolymers Verduzco, Rafael; Li, Xianyu; Pesek, Stacy L. Chemical Society Reviews, Vol. 44, Issue 8 https://doi.org/10.1039/C4CS00329B	journal	January 2015
Theory of the Interface between Immiscible Polymers. II Helfand, Eugene; Tagami, Yukiko The Journal of Chemical Physics, Vol. 56, Issue 7 https://doi.org/10.1063/1.1677735	journal	April 1972
Thin films of block copolymer Matsen, M. W. The Journal of Chemical Physics, Vol. 106, Issue 18 https://doi.org/10.1063/1.473778	journal	May 1997
Symmetric diblock copolymers in thin films. I. Phase stability in self-consistent field calculations and Monte Carlo simulations Geisinger, T.; Müller, M.; Binder, K. The Journal of Chemical Physics, Vol. 111, Issue 11 https://doi.org/10.1063/1.479778	journal	September 1999
Rapid self-assembly of brush block copolymers to photonic crystals Sveinbjornsson, B. R.; Weitekamp, R. A.; Miyake, G. M. Proceedings of the National Academy of Sciences, Vol. 109, Issue 36, p. 14332-14336 https://doi.org/10.1073/pnas.1213055109	journal	August 2012
Morphology, directed self-assembly and pattern transfer from a high molecular weight polystyrene-block-poly(dimethylsiloxane) block copolymer film Cheng, Li-Chen; Bai, Wubin; Fernandez Martin, Eduardo Nanotechnology, Vol. 28, Issue 14 https://doi.org/10.1088/1361-6528/aa61c9	journal	March 2017
Fifty Years of Moore's Law Mack, Chris A. IEEE Transactions on Semiconductor Manufacturing, Vol. 24, Issue 2 https://doi.org/10.1109/TSM.2010.2096437	journal	May 2011
Large-area achromatic interferometric lithography for 100 nm period gratings and grids Savas, T. A. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 14, Issue 6 https://doi.org/10.1116/1.588613	journal	November 1996
Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates Bita, I.; Yang, J. K. W.; Jung, Y. S. Science, Vol. 321, Issue 5891 https://doi.org/10.1126/science.1159352	journal	August 2008
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
Automated Defect and Correlation Length Analysis of Block Copolymer Thin Film Nanopatterns Murphy, Jeffrey N.; Harris, Kenneth D.; Buriak, Jillian M. PLOS ONE, Vol. 10, Issue 7 https://doi.org/10.1371/journal.pone.0133088	journal	July 2015

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