Double-Layer Morphologies from a Silicon-Containing ABA Triblock Copolymer

Lee, Sangho; Cheng, Li-Chen; Gadelrab, Karim R.; Ntetsikas, Konstantinos; Moschovas, Dimitrios; Yager, Kevin G.; Avgeropoulos, Apostolos; Alexander-Katz, Alfredo; Ross, Caroline A.

doi:10.1021/acsnano.8b02851

Double-Layer Morphologies from a Silicon-Containing ABA Triblock Copolymer

Journal Article · Fri Jun 01 00:00:00 EDT 2018 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.8b02851· OSTI ID:1467847

^[1]; ^[1]; ^[1]; ^[2]; Moschovas, Dimitrios ^[2]; ^[3]; ^[2]; Alexander-Katz, Alfredo ^[1]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Univ. of Ioannina (Greece). Dept. of Materials Science and Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)

A combined experimental and self-consistent-field theoretical (SCFT) investigation of the phase behavior of poly(stryrene-b-dimethylsiloxane-b-styrene) (PS-b-PDMS-b-PS, or SDS32) thin films during solvent vapor annealing is presented. The morphology of the triblock copolymer is described as a function of the as-cast film thickness and the ratio of two different solvent vapors, toluene and heptane. SDS32 formed terraced bilayer morphologies even when the film thickness was much lower than the commensurate thickness. The morphology transitioned between bilayer cylinders, bilayer perforated lamellae, and bilayer lamellae, including mixed structures such as a perforated lamella on top of a layer of in-plane cylinders, as the heptane fraction during solvent annealing increased. SCFT modeling showed the same morphological trends as a function of the block volume fraction. In comparison with diblock PS-b-PDMS with the same molecular weight, the SDS32 offers a simple route to produce a diversity of well-ordered bilayer structures with smaller feature sizes, including the formation of bilayer perforated lamellae over a large process window.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1467847

Report Number(s):: BNL--208016-2018-JAAM

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 6 Vol. 12; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (60)

Self-Assembly Approaches to Three-Dimensional Photonic Crystals Xia, Y.; Gates, B.; Li, Z. -Y. Advanced Materials, Vol. 13, Issue 6 https://doi.org/10.1002/1521-4095(200103)13:6<409::AID-ADMA409>3.0.CO;2-C	journal	March 2001
Formation of a Cobalt Magnetic Dot Array via Block Copolymer Lithography Cheng, J.Y.; Ross, C.A.; Chan, V.Z.-H. Advanced Materials, Vol. 13, Issue 15, p. 1174-1178 https://doi.org/10.1002/1521-4095(200108)13:15<1174::AID-ADMA1174>3.0.CO;2-Q	journal	August 2001
Densely Packed Arrays of Ultra-High-Aspect-Ratio Silicon Nanowires Fabricated using Block-Copolymer Lithography and Metal-Assisted Etching Chang, Shih-Wei; Chuang, Vivian P.; Boles, Steven T. Advanced Functional Materials, Vol. 19, Issue 15, p. 2495-2500 https://doi.org/10.1002/adfm.200900181	journal	August 2009
Block Copolymers as a Tool for Nanomaterial Fabrication Lazzari, M.; López-Quintela, M. A. Advanced Materials, Vol. 15, Issue 19 https://doi.org/10.1002/adma.200300382	journal	October 2003
Universal Block Copolymer Lithography for Metals, Semiconductors, Ceramics, and Polymers Jeong, Seong-Jun; Xia, Guodong; Kim, Bong Hoon Advanced Materials, Vol. 20, Issue 10 https://doi.org/10.1002/adma.200702930	journal	May 2008
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
Directed Self-Assembly of Poly(2-vinylpyridine)- b -polystyrene- b -poly(2-vinylpyridine) Triblock Copolymer with Sub-15 nm Spacing Line Patterns Using a Nanoimprinted Photoresist Template Sun, Zhiwei; Chen, Zhenbin; Zhang, Wenxu Advanced Materials, Vol. 27, Issue 29 https://doi.org/10.1002/adma.201501585	journal	June 2015
Highly Ordered Nanoring Arrays Formed by Templated Si-Containing Triblock Terpolymer Thin Films Aissou, Karim; Mumtaz, Muhammad; Marcasuzaa, Pierre Small, Vol. 13, Issue 12 https://doi.org/10.1002/smll.201603184	journal	January 2017
Parallel algorithm for numerical self-consistent field theory simulations of block copolymer structure Sides, Scott W.; Fredrickson, Glenn H. Polymer, Vol. 44, Issue 19 https://doi.org/10.1016/S0032-3861(03)00606-2	journal	September 2003
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
Interfacial Energy-Controlled Top Coats for Gyroid/Cylinder Phase Transitions of Polystyrene- block -polydimethylsiloxane Block Copolymer Thin Films Ryu, In Hyu; Kim, Yong Joo; Jung, Yeon Sik ACS Applied Materials & Interfaces, Vol. 9, Issue 20 https://doi.org/10.1021/acsami.7b02910	journal	May 2017
The Limits of Lamellae-Forming PS- b -PMMA Block Copolymers for Lithography Wan, Lei; Ruiz, Ricardo; Gao, He ACS Nano, Vol. 9, Issue 7 https://doi.org/10.1021/acsnano.5b02613	journal	June 2015
Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing Xiong, Shisheng; Wan, Lei; Ishida, Yoshihito ACS Nano, Vol. 10, Issue 8 https://doi.org/10.1021/acsnano.6b03667	journal	July 2016
Structural Color for Additive Manufacturing: 3D-Printed Photonic Crystals from Block Copolymers Boyle, Bret M.; French, Tracy A.; Pearson, Ryan M. ACS Nano, Vol. 11, Issue 3 https://doi.org/10.1021/acsnano.7b00032	journal	February 2017
Self-Registered Self-Assembly of Block Copolymers Wan, Lei; Ruiz, Ricardo; Gao, He ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b03284	journal	July 2017
Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush Lin, Tzu-Pin; Chang, Alice B.; Luo, Shao-Xiong ACS Nano, Vol. 11, Issue 11 https://doi.org/10.1021/acsnano.7b06664	journal	September 2017
Unexpected Consequences of Block Polydispersity on the Self-Assembly of ABA Triblock Copolymers Widin, Joan M.; Schmitt, Adam K.; Schmitt, Andrew L. Journal of the American Chemical Society, Vol. 134, Issue 8 https://doi.org/10.1021/ja210548e	journal	February 2012
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
Field-Theoretic Computer Simulation Methods for Polymers and Complex Fluids Fredrickson, Glenn H.; Ganesan, Venkat; Drolet, François Macromolecules, Vol. 35, Issue 1 https://doi.org/10.1021/ma011515t	journal	January 2002
Novel Inorganic−Organic Hybrid Block Copolymers as Pore Generators for Nanoporous Ultralow-Dielectric-Constant Films Ro, Hyun Wook; Kim, Kook Ji; Theato, Patrick Macromolecules, Vol. 38, Issue 3 https://doi.org/10.1021/ma048353w	journal	January 2005
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
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
Efficient Electrochromic Devices Made from 3D Nanotubular Gyroid Networks Scherer, Maik R. J.; Steiner, Ullrich Nano Letters, Vol. 13, Issue 7 https://doi.org/10.1021/nl303833h	journal	December 2012
Solvothermal Annealing of Block Copolymer Thin Films Gotrik, Kevin W.; Ross, C. A. Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl4021683	journal	October 2013
Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration Jackson, Elizabeth A.; Hillmyer, Marc A. ACS Nano, Vol. 4, Issue 7 https://doi.org/10.1021/nn1014006	journal	June 2010
Systematic Study on the Effect of Solvent Removal Rate on the Morphology of Solvent Vapor Annealed ABA Triblock Copolymer Thin Films Albert, Julie N. L.; Young, Wen-Shiue; Lewis, Ronald L. ACS Nano, Vol. 6, Issue 1 https://doi.org/10.1021/nn203776c	journal	December 2011
Directed Assembly of Non-equilibrium ABA Triblock Copolymer Morphologies on Nanopatterned Substrates Ji, Shengxiang; Nagpal, Umang; Liu, Guoliang ACS Nano, Vol. 6, Issue 6 https://doi.org/10.1021/nn301306v	journal	May 2012
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
Spatial and Orientation Control of Cylindrical Nanostructures in ABA Triblock Copolymer Thin Films by Raster Solvent Vapor Annealing Seppala, Jonathan E.; Lewis, Ronald L.; Epps, Thomas H. ACS Nano, Vol. 6, Issue 11 https://doi.org/10.1021/nn303416p	journal	October 2012
Conversion of Bilayers of PS- b -PDMS Block Copolymer into Closely Packed, Aligned Silica Nanopatterns Wu, Nathanael L. Y.; Harris, Kenneth D.; Buriak, Jillian M. ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn401968t	journal	May 2013
Nanoporous Block Copolymer Membranes for Ultrafiltration: A Simple Approach to Size Tunability Ahn, Hyungju; Park, Sungmin; Kim, Sang-Woo ACS Nano, Vol. 8, Issue 11 https://doi.org/10.1021/nn505234v	journal	November 2014
Robust Block Copolymer Mask for Nanopatterning Polymer Films Chao, Chia-Cheng; Wang, Tzu-Chung; Ho, Rong-Ming ACS Nano, Vol. 4, Issue 4 https://doi.org/10.1021/nn901370g	journal	March 2010
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
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
Engineering the surface structure of MoS₂ to preferentially expose active edge sites for electrocatalysis Kibsgaard, Jakob; Chen, Zhebo; Reinecke, Benjamin N. Nature Materials, Vol. 11, Issue 11, p. 963-969 https://doi.org/10.1038/nmat3439	journal	October 2012
Self-assembly of functional nanostructures from ABC triblock copolymers Ludwigs, Sabine; Böker, Alexander; Voronov, Andrej Nature Materials, Vol. 2, Issue 11 https://doi.org/10.1038/nmat997	journal	October 2003
Graphene nanomesh Bai, Jingwei; Zhong, Xing; Jiang, Shan Nature Nanotechnology, Vol. 5, Issue 3 https://doi.org/10.1038/nnano.2010.8	journal	February 2010
Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat Suh, Hyo Seon; Kim, Do Han; Moni, Priya Nature Nanotechnology, Vol. 12, Issue 6 https://doi.org/10.1038/nnano.2017.34	journal	March 2017
Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns Chang, Tzu-Hsuan; Xiong, Shisheng; Jacobberger, Robert M. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep31407	journal	August 2016
Block copolymer self-assembly for nanophotonics Stefik, Morgan; Guldin, Stefan; Vignolini, Silvia Chemical Society Reviews, Vol. 44, Issue 15 https://doi.org/10.1039/C4CS00517A	journal	January 2015
Synthesis, molecular characterization and self-assembly of (PS-b-PDMS) _n type linear (n = 1, 2) and star (n = 3, 4) block copolymers Georgopanos, Prokopios; Lo, Ting-Ya; Ho, Rong-Ming Polymer Chemistry, Vol. 8, Issue 5 https://doi.org/10.1039/C6PY01768A	journal	January 2017
Miktoarm star polymers: advances in synthesis, self-assembly, and applications Khanna, Kunal; Varshney, Sunil; Kakkar, Ashok Polymer Chemistry, Vol. 1, Issue 8 https://doi.org/10.1039/c0py00082e	journal	January 2010
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
Bit patterned media based on block copolymer directed assembly with narrow magnetic switching field distribution Hellwig, O.; Bosworth, J. K.; Dobisz, E. Applied Physics Letters, Vol. 96, Issue 5 https://doi.org/10.1063/1.3293301	journal	February 2010
Equilibrium behavior of symmetric ABA triblock copolymer melts Matsen, M. W.; Thompson, R. B. The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480006	journal	October 1999
Universal pattern transfer methods for metal nanostructures by block copolymer lithography Tu, Kun-Hua; Bai, Wubin; Liontos, George Nanotechnology, Vol. 26, Issue 37 https://doi.org/10.1088/0957-4484/26/37/375301	journal	August 2015
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
Magnetic nanostructures from block copolymer lithography: Hysteresis, thermal stability, and magnetoresistance Cheng, J. Y.; Jung, W.; Ross, C. A. Physical Review B, Vol. 70, Issue 6 https://doi.org/10.1103/PhysRevB.70.064417	journal	August 2004
Efficient computation of the structural phase behavior of block copolymers Tzeremes, G.; Rasmussen, K. Ø.; Lookman, T. Physical Review E, Vol. 65, Issue 4 https://doi.org/10.1103/PhysRevE.65.041806	journal	April 2002
Phase Behavior in Thin Films of Cylinder-Forming Block Copolymers Knoll, A.; Horvat, A.; Lyakhova, K. S. Physical Review Letters, Vol. 89, Issue 3 https://doi.org/10.1103/PhysRevLett.89.035501	journal	June 2002
Bit-Patterned Magnetic Recording: Theory, Media Fabrication, and Recording Performance Albrecht, Thomas R.; Arora, Hitesh; Ayanoor-Vitikkate, Vipin IEEE Transactions on Magnetics, Vol. 51, Issue 5 https://doi.org/10.1109/TMAG.2015.2397880	journal	May 2015
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
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
Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays Tang, C.; Lennon, E. M.; Fredrickson, G. H. Science, Vol. 322, Issue 5900 https://doi.org/10.1126/science.1162950	journal	October 2008
Block Copolymer Self-Assembly–Directed Single-Crystal Homo- and Heteroepitaxial Nanostructures Arora, Hitesh; Du, Phong; Tan, Kwan W. Science, Vol. 330, Issue 6001, p. 214-219 https://doi.org/10.1126/science.1193369	journal	October 2010
Block Copolymer Lithography: Periodic Arrays of 10¹¹ Holes in 1 Square Centimeter Park, Miri; Harrison, Christopher; Chaikin, Paul M. Science, Vol. 276, Issue 5317, p. 1401-1404 https://doi.org/10.1126/science.276.5317.1401	journal	May 1997
Ultrahigh-Density Nanowire Arrays Grown in Self-Assembled Diblock Copolymer Templates Thurn-Albrecht, T.; Schotter, J.; Kastle, G. A. Science, Vol. 290, Issue 5499, p. 2126-2129 https://doi.org/10.1126/science.290.5499.2126	journal	December 2000
Transient laser heating induced hierarchical porous structures from block copolymer–directed self-assembly Tan, Kwan Wee; Jung, Byungki; Werner, Jörg G. Science, Vol. 349, Issue 6243 https://doi.org/10.1126/science.aab0492	journal	July 2015
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

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36 MATERIALS SCIENCE
77 NANOSCIENCE AND NANOTECHNOLOGY
ABA triblock copolymer
PS-b-PDMS-b-PS
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thin film

Double-Layer Morphologies from a Silicon-Containing ABA Triblock Copolymer

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