Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films
Abstract

Block copolymers spontaneously form well-defined nanoscale morphologies during thermal annealing. Yet, the structures one obtains can be influenced by nonequilibrium effects, including processing history or pathway-dependent assembly. Here, we explore various pathways for ordering of block copolymer thin films, using oven-annealing, as well as newly disclosed methods for rapid photothermal annealing and photothermal shearing. We report the discovery of an efficient pathway for ordering self-assembled films: ultrarapid shearing of as-cast films induces “latent alignment” in the disordered morphology. Subsequent thermal processing can then develop this directly into a uniaxially aligned morphology with low defect density. This deeper understanding of pathway-dependence may have broad implications in self-assembly.
Cited By
This article is cited by 47 publications.
- Hyun Su Yun, Dong Hwan Kim, Hong Gu Kwon, Hong Kyoon Choi. Centrifugal Force-Induced Alignment in the Self-Assembly of Block Copolymers. Macromolecules 2022, 55 (11) , 4305-4312. https://doi.org/10.1021/acs.macromol.2c00325
- Geon Gug Yang, Hee Jae Choi, Kyu Hyo Han, Jang Hwan Kim, Chan Woo Lee, Edwin Ino Jung, Hyeong Min Jin, Sang Ouk Kim. Block Copolymer Nanopatterning for Nonsemiconductor Device Applications. ACS Applied Materials & Interfaces 2022, 14 (10) , 12011-12037. https://doi.org/10.1021/acsami.1c22836
- Xiaokang Sun, Kai Liu, Nie Zhao, Fenggang Bian, Chunming Yang, Yuying Huang. In Situ Grazing-Incidence SAXS Investigation of Thermal-Induced Self-Assembly Process of PS-b-PMMA Films Deposited on Surface-Modified Substrate. The Journal of Physical Chemistry B 2022, 126 (7) , 1625-1632. https://doi.org/10.1021/acs.jpcb.1c09443
- Eric R. Gottlieb, Panagiotis Dimitrakellis, Dionisios G. Vlachos, Thomas H. Epps, III. Inline Rolling Shear Alignment: Deposition and Long-Range Order of Block Polymer Templates in a Fast, Single-Step Process. ACS Applied Polymer Materials 2022, 4 (1) , 682-691. https://doi.org/10.1021/acsapm.1c01580
- Eric R. Gottlieb, Aynur Guliyeva, Thomas H. Epps, III. From Lab to Fab: Enabling Enhanced Control of Block Polymer Thin-Film Nanostructures. ACS Applied Polymer Materials 2021, 3 (9) , 4288-4303. https://doi.org/10.1021/acsapm.1c00680
- Jinwoo Oh, Minkyung Shin, In Soo Kim, Hyo Seon Suh, YongJoo Kim, Jai Kyeong Kim, Joona Bang, Bongjun Yeom, Jeong Gon Son. Shear-Rolling Process for Unidirectionally and Perpendicularly Oriented Sub-10-nm Block Copolymer Patterns on the 4 in Scale. ACS Nano 2021, 15 (5) , 8549-8558. https://doi.org/10.1021/acsnano.1c00358
- Anabella A. Abate, Cristian M. Piqueras, Daniel A. Vega. Defect-Induced Order–Order Phase Transition in Triblock Copolymer Thin Films. Macromolecules 2021, 54 (4) , 1639-1647. https://doi.org/10.1021/acs.macromol.0c02593
- Dakyung Lee, Junyoung Lee, Jinhwi Park, Taihyun Chang. Orientation of Microphase in Polystyrene-b-polyisoprene Thin Film under Solvent Vapor Annealing. Macromolecules 2020, 53 (21) , 9611-9618. https://doi.org/10.1021/acs.macromol.0c01017
- Arkadiusz A. Leniart, Przemyslaw Pula, Andrzej Sitkiewicz, Pawel W. Majewski. Macroscopic Alignment of Block Copolymers on Silicon Substrates by Laser Annealing. ACS Nano 2020, 14 (4) , 4805-4815. https://doi.org/10.1021/acsnano.0c00696
- Gregory S. Doerk, Ruipeng Li, Masafumi Fukuto, Kevin G. Yager. Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly. Macromolecules 2020, 53 (3) , 1098-1113. https://doi.org/10.1021/acs.macromol.9b02296
- Monali N. Basutkar, Pawel W. Majewski, Gregory S. Doerk, Kristof Toth, Chinedum O. Osuji, Alamgir Karim, Kevin G. Yager. Aligned Morphologies in Near-Edge Regions of Block Copolymer Thin Films. Macromolecules 2019, 52 (19) , 7224-7233. https://doi.org/10.1021/acs.macromol.9b01703
- Gregory S. Doerk, Ruipeng Li, Masafumi Fukuto, Alfredo Rodriguez, Kevin G. Yager. Thickness-Dependent Ordering Kinetics in Cylindrical Block Copolymer/Homopolymer Ternary Blends. Macromolecules 2018, 51 (24) , 10259-10270. https://doi.org/10.1021/acs.macromol.8b01773
- Jaewon Choi, Yinyong Li, Paul Y. Kim, Feng Liu, Hyeyoung Kim, Duk Man Yu, June Huh, Kenneth R. Carter, Thomas P. Russell. Orthogonally Aligned Block Copolymer Line Patterns on Minimal Topographic Patterns. ACS Applied Materials & Interfaces 2018, 10 (9) , 8324-8332. https://doi.org/10.1021/acsami.7b17713
- Gregory S. Doerk and Kevin G. Yager . Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends. ACS Nano 2017, 11 (12) , 12326-12336. https://doi.org/10.1021/acsnano.7b06154
- Cameron K. Shelton, Ronald L. Jones, and Thomas H. Epps, III . Kinetics of Domain Alignment in Block Polymer Thin Films during Solvent Vapor Annealing with Soft Shear: An in Situ Small-Angle Neutron Scattering Investigation. Macromolecules 2017, 50 (14) , 5367-5376. https://doi.org/10.1021/acs.macromol.7b00876
- Cong Jin, Brian C. Olsen, Erik J. Luber, and Jillian M. Buriak . Nanopatterning via Solvent Vapor Annealing of Block Copolymer Thin Films. Chemistry of Materials 2017, 29 (1) , 176-188. https://doi.org/10.1021/acs.chemmater.6b02967
- Saumil Samant, Joseph Strzalka, Kevin G. Yager, Kim Kisslinger, Danielle Grolman, Monali Basutkar, Namrata Salunke, Gurpreet Singh, Brian Berry, and Alamgir Karim . Ordering Pathway of Block Copolymers under Dynamic Thermal Gradients Studied by in Situ GISAXS. Macromolecules 2016, 49 (22) , 8633-8642. https://doi.org/10.1021/acs.macromol.6b01555
- Kehua Lin, Yuanqing Gu, Huan Zhang, Zhe Qiang, Bryan D. Vogt, and Nicole S. Zacharia . Accelerated Amidization of Branched Poly(ethylenimine)/Poly(acrylic acid) Multilayer Films by Microwave Heating. Langmuir 2016, 32 (36) , 9118-9125. https://doi.org/10.1021/acs.langmuir.6b02051
- Alan G. Jacobs, Clemens Liedel, Hui Peng, Linxi Wang, Detlef-M. Smilgies, Christopher K. Ober, and Michael O. Thompson . Kinetics of Block Copolymer Phase Segregation during Sub-millisecond Transient Thermal Annealing. Macromolecules 2016, 49 (17) , 6462-6470. https://doi.org/10.1021/acs.macromol.6b00698
- Hyeong Min Jin, Seung Hyun Lee, Ju Young Kim, Seung-Woo Son, Bong Hoon Kim, Hwan Keon Lee, Jeong Ho Mun, Seung Keun Cha, Jun Soo Kim, Paul F. Nealey, Keon Jae Lee, and Sang Ouk Kim . Laser Writing Block Copolymer Self-Assembly on Graphene Light-Absorbing Layer. ACS Nano 2016, 10 (3) , 3435-3442. https://doi.org/10.1021/acsnano.5b07511
- Su Eon Lee, Simon Kim, Jun Hyun Park, Ho Jun Jin, Hwa Soo Kim, Jang Hwan Kim, Hyeong Min Jin, Bong Hoon Kim. Directed self‐assembly of block copolymer thin films via momentary thickness gradients. Journal of Polymer Science 2023, https://doi.org/10.1002/pol.20230254
- Alessandro Angelini, Anja Car, Ionel Adrian Dinu, Luigi Leva, Wilfredo Yave. Amphiphilic Poly(vinyl alcohol) Membranes Leaving Out Chemical Cross‐Linkers: Design, Synthesis, and Function of Tailor‐Made Poly(vinyl alcohol)‐ b ‐poly(styrene) Copolymers. Macromolecular Rapid Communications 2023, 44 (16) https://doi.org/10.1002/marc.202200875
- Sebastian T. Russell, Suwon Bae, Ashwanth Subramanian, Nikhil Tiwale, Gregory Doerk, Chang-Yong Nam, Masafumi Fukuto, Kevin G. Yager. Priming self-assembly pathways by stacking block copolymers. Nature Communications 2022, 13 (1) https://doi.org/10.1038/s41467-022-34729-0
- Shuhui Ma, Yushuang Hou, Jinlin Hao, Cuncai Lin, Jiawei Zhao, Xin Sui. Well-Defined Nanostructures by Block Copolymers and Mass Transport Applications in Energy Conversion. Polymers 2022, 14 (21) , 4568. https://doi.org/10.3390/polym14214568
- Hyeong Min Jin, Su Eon Lee, Simon Kim, Ju Young Kim, Young‐Soo Han, Bong Hoon Kim. Directed high‐χ block copolymer self‐assembly by laser writing on silicon substrate. Journal of Applied Polymer Science 2022, 139 (23) https://doi.org/10.1002/app.52291
- Jean-Sebastien Benas, Fang-Cheng Liang, Wei-Cheng Chen, Chung-Wei Hung, Jung-Yao Chen, Ye Zhou, Su-Ting Han, Redouane Borsali, Chi-Ching Kuo. Lewis adduct approach for self-assembled block copolymer perovskite quantum dots composite toward optoelectronic application: Challenges and prospects. Chemical Engineering Journal 2022, 431 , 133701. https://doi.org/10.1016/j.cej.2021.133701
- Mark Robertson, Qingya Zhou, Changhuai Ye, Zhe Qiang. Developing Anisotropy in Self‐Assembled Block Copolymers: Methods, Properties, and Applications. Macromolecular Rapid Communications 2021, 42 (17) , 2100300. https://doi.org/10.1002/marc.202100300
- Min Koo, Hyowon Han, Jin Woo Oh, Cheolmin Park. Photon-assisted nanostructures of self-assembled soft materials. Nano Today 2021, 38 , 101199. https://doi.org/10.1016/j.nantod.2021.101199
- Kangho Park, Hyeong Min Jin, Kiok Kwon, Jang Hwan Kim, Haeju Yun, Kyu Hyo Han, Taeyeong Yun, Sang Ouk Kim, Hee‐Tae Jung. Large‐Area Alignment of Supramolecular Columns by Photothermal Laser Writing. Advanced Materials 2020, 32 (36) https://doi.org/10.1002/adma.202002620
- Gabriele Seguini, Fabio Zanenga, Gianluca Cannetti, Michele Perego. Thermodynamics and ordering kinetics in asymmetric PS- b -PMMA block copolymer thin films. Soft Matter 2020, 16 (23) , 5525-5533. https://doi.org/10.1039/D0SM00441C
- Samantha R. Nowak, Kevin G. Yager. Photothermally Directed Assembly of Block Copolymers. Advanced Materials Interfaces 2020, 7 (5) https://doi.org/10.1002/admi.201901679
- Marcus Müller. Process-directed self-assembly of copolymers: Results of and challenges for simulation studies. Progress in Polymer Science 2020, 101 , 101198. https://doi.org/10.1016/j.progpolymsci.2019.101198
- Ye Chan Kim, Tae Joo Shin, Su-Mi Hur, Seok Joon Kwon, So Youn Kim. Shear-solvo defect annihilation of diblock copolymer thin films over a large area. Science Advances 2019, 5 (6) https://doi.org/10.1126/sciadv.aaw3974
- Bingbing Yue, Xin Jin, Pei Zhao, Mingjie Zhu, Liangliang Zhu. Directed Self‐Assembly of Templatable Block Copolymers by Easily Accessible Magnetic Control. Small 2019, 15 (7) https://doi.org/10.1002/smll.201804572
- Liangshun Zhang, Lingling Liu, Jiaping Lin. Well-ordered self-assembled nanostructures of block copolymer films via synergistic integration of chemoepitaxy and zone annealing. Physical Chemistry Chemical Physics 2018, 20 (1) , 498-508. https://doi.org/10.1039/C7CP06261C
- Youngwoo Choo, Paweł W. Majewski, Masafumi Fukuto, Chinedum O. Osuji, Kevin G. Yager. Pathway-engineering for highly-aligned block copolymer arrays. Nanoscale 2018, 10 (1) , 416-427. https://doi.org/10.1039/C7NR06069F
- Samuel M Nicaise, Karim R Gadelrab, Amir Tavakkoli K G, Caroline A Ross, Alfredo Alexander-Katz, Karl K Berggren. Rapid shear alignment of sub-10 nm cylinder-forming block copolymer films based on thermal expansion mismatch. Nano Futures 2017, 1 (3) , 035006. https://doi.org/10.1088/2399-1984/aaa068
- Jonathan Phillip Singer. Thermocapillary approaches to the deliberate patterning of polymers. Journal of Polymer Science Part B: Polymer Physics 2017, 55 (22) , 1649-1668. https://doi.org/10.1002/polb.24298
- Hyeong Min Jin, Dae Yong Park, Seong‐Jun Jeong, Gil Yong Lee, Ju Young Kim, Jeong Ho Mun, Seung Keun Cha, Joonwon Lim, Jun Soo Kim, Kwang Ho Kim, Keon Jae Lee, Sang Ouk Kim. Flash Light Millisecond Self‐Assembly of High χ Block Copolymers for Wafer‐Scale Sub‐10 nm Nanopatterning. Advanced Materials 2017, 29 (32) https://doi.org/10.1002/adma.201700595
- Theyencheri Narayanan, Hanna Wacklin, Oleg Konovalov, Reidar Lund. Recent applications of synchrotron radiation and neutrons in the study of soft matter. Crystallography Reviews 2017, 23 (3) , 160-226. https://doi.org/10.1080/0889311X.2016.1277212
- Xiaomin Wan, Tong Gao, Liangshun Zhang, Jiaping Lin. Ordering kinetics of lamella-forming block copolymers under the guidance of various external fields studied by dynamic self-consistent field theory. Physical Chemistry Chemical Physics 2017, 19 (9) , 6707-6720. https://doi.org/10.1039/C6CP08726D
- Yanfeng Xia, Zhe Qiang, Byeongdu Lee, Matthew L. Becker, Bryan D. Vogt. Solid state microwave synthesis of highly crystalline ordered mesoporous hausmannite Mn 3 O 4 films. CrystEngComm 2017, 19 (30) , 4294-4303. https://doi.org/10.1039/C7CE00900C
- Gregory S. Doerk, Kevin G. Yager. Beyond native block copolymer morphologies. Molecular Systems Design & Engineering 2017, 2 (5) , 518-538. https://doi.org/10.1039/C7ME00069C
- Jaewon Choi, Ilja Gunkel, Yinyong Li, Zhiwei Sun, Feng Liu, Hyeyoung Kim, Kenneth R. Carter, Thomas P. Russell. Macroscopically ordered hexagonal arrays by directed self-assembly of block copolymers with minimal topographic patterns. Nanoscale 2017, 9 (39) , 14888-14896. https://doi.org/10.1039/C7NR05394K
- Pawel W Majewski, Kevin G Yager. Rapid ordering of block copolymer thin films. Journal of Physics: Condensed Matter 2016, 28 (40) , 403002. https://doi.org/10.1088/0953-8984/28/40/403002
- Zhe Qiang, Changhuai Ye, Kehua Lin, Matthew L. Becker, Kevin A. Cavicchi, Bryan D. Vogt. Evolution in surface morphology during rapid microwave annealing of PS ‐ b ‐ PMMA thin films. Journal of Polymer Science Part B: Polymer Physics 2016, 54 (15) , 1499-1506. https://doi.org/10.1002/polb.24043
- Pawel W. Majewski, Kevin G. Yager. Reordering transitions during annealing of block copolymer cylinder phases. Soft Matter 2016, 12 (1) , 281-294. https://doi.org/10.1039/C5SM02441B