Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films
Abstract

As demand for smaller, more powerful, and energy-efficient devices continues, conventional patterning technologies are pushing up against fundamental limits. Block copolymers (BCPs) are considered prime candidates for a potential solution via directed self-assembly of nanostructures. We introduce here a facile directed self-assembly method to rapidly fabricate unidirectionally aligned BCP nanopatterns at large scale, on rigid or flexible template-free substrates via a thermally induced dynamic gradient soft-shear field. A localized differential thermal expansion at the interface between a BCP film and a confining polydimethylsiloxane (PDMS) layer due to a dynamic thermal field imposes the gradient soft-shear field. PDMS undergoes directional expansion (along the annealing direction) in the heating zone and contracts back in the cooling zone, thus setting up a single cycle of oscillatory shear (maximum lateral shear stress ∼12 × 104 Pa) in the system. We successfully apply this process to create unidirectional alignment of BCP thin films over a wide range of thicknesses (nm to μm) and processing speeds (μm/s to mm/s) using both a flat and patterned PDMS layer. Grazing incidence small-angle X-ray scattering measurements show absolutely no sign of isotropic population and reveal ≥99% aligned orientational order with an angular spread Δθfwhm ≤ 5° (full width at half-maximum). This method may pave the way to practical industrial use of hierarchically patterned BCP nanostructures.
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- 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
- Ali Masud, Melanie Longanecker, Sonal Bhadauriya, Maninderjeet Singh, Wenjie Wu, Kshitij Sharma, Tanguy Terlier, Abdullah M. Al-Enizi, Sushil Satija, Jack F. Douglas, Alamgir Karim. Ionic Liquid Enhanced Parallel Lamellar Ordering in Block Copolymer Films. Macromolecules 2021, 54 (10) , 4531-4545. https://doi.org/10.1021/acs.macromol.0c02546
- 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
- Maninderjeet Singh, Wenjie Wu, Monali N. Basutkar, Joseph Strzalka, Abdullah M. Al-Enizi, Jack F. Douglas, Alamgir Karim. Ultra-Fast Vertical Ordering of Lamellar Block Copolymer Films on Unmodified Substrates. Macromolecules 2021, 54 (3) , 1564-1573. https://doi.org/10.1021/acs.macromol.0c01782
- Saumil Samant, Monali Basutkar, Maninderjeet Singh, Ali Masud, Christopher A. Grabowski, Kim Kisslinger, Joseph Strzalka, Guangcui Yuan, Sushil Satija, Ikeoluwa Apata, Dharmaraj Raghavan, Michael Durstock, Alamgir Karim. Effect of Molecular Weight and Layer Thickness on the Dielectric Breakdown Strength of Neat and Homopolymer Swollen Lamellar Block Copolymer Films. ACS Applied Polymer Materials 2020, 2 (8) , 3072-3083. https://doi.org/10.1021/acsapm.0c00127
- 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
- Joseph D. Hill, Paul C. Millett. Directed Self-Assembly in Diblock Copolymer Thin Films for Uniform Hemisphere Pattern Formation. Macromolecules 2019, 52 (24) , 9495-9503. https://doi.org/10.1021/acs.macromol.9b01545
- Anabella A. Abate, Giang Thi Vu, Cristian M. Piqueras, María Cecilia del Barrio, Leopoldo R. Gómez, Gabriel Catalini, Friederike Schmid, Daniel A. Vega. Order–Order Phase Transitions Induced by Supercritical Carbon Dioxide in Triblock Copolymer Thin Films. Macromolecules 2019, 52 (20) , 7786-7797. https://doi.org/10.1021/acs.macromol.9b01278
- 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
- Yuma Morimitsu, Daniel Salatto, Naisheng Jiang, Mani Sen, Shotaro Nishitsuji, Benjamin M. Yavitt, Maya K. Endoh, Ashwanth Subramanian, Chang-Yong Nam, Ruipeng Li, Masafumi Fukuto, Yugang Zhang, Lutz Wiegart, Andrei Fluerasu, Keiji Tanaka, Tadanori Koga. “Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films. Macromolecules 2019, 52 (14) , 5157-5167. https://doi.org/10.1021/acs.macromol.9b00597
- Edward W. Malachosky, Alexander Filatov, Philippe Guyot-Sionnest. Enhanced Corrugation and Chemical Contrast of Diblock Copolymer Films by Sequential Solvent Exposures. The Journal of Physical Chemistry C 2018, 122 (40) , 23117-23122. https://doi.org/10.1021/acs.jpcc.8b04461
- Chao Zhang, Kevin A. Cavicchi, Ruipeng Li, Kevin G. Yager, Masafumi Fukuto, Bryan D. Vogt. Thickness Limit for Alignment of Block Copolymer Films Using Solvent Vapor Annealing with Shear. Macromolecules 2018, 51 (11) , 4213-4219. https://doi.org/10.1021/acs.macromol.8b00539
- Xiangyu Liu, Nandini Bhandaru, Meneka Banik, Xiaoteng Wang, Abdullah M. Al-Enizi, Alamgir Karim, and Rabibrata Mukherjee . Capillary Force Lithography Pattern-Directed Self-Assembly (CFL-PDSA) of Phase-Separating Polymer Blend Thin Films. ACS Omega 2018, 3 (2) , 2161-2168. https://doi.org/10.1021/acsomega.7b02078
- 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
- Ye Chan Kim, Dong Hyup Kim, Se Hun Joo, Na Kyung Kwon, Tae Joo Shin, Richard A. Register, Sang Kyu Kwak, and So Youn Kim . Log-Rolling Block Copolymer Cylinders. Macromolecules 2017, 50 (9) , 3607-3616. https://doi.org/10.1021/acs.macromol.6b02516
- Lamiaa G. Alharbe, Richard A. Register, and Jamie K. Hobbs . Orientation Control and Crystallization in a Soft Confined Phase Separated Block Copolymer. Macromolecules 2017, 50 (3) , 987-996. https://doi.org/10.1021/acs.macromol.6b02361
- 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
- Anabella A. Abate, Giang Thi Vu, Aldo D. Pezzutti, Nicolás A. García, Raleigh L. Davis, Friederike Schmid, Richard A. Register, and Daniel A. Vega . Shear-Aligned Block Copolymer Monolayers as Seeds To Control the Orientational Order in Cylinder-Forming Block Copolymer Thin Films. Macromolecules 2016, 49 (19) , 7588-7596. https://doi.org/10.1021/acs.macromol.6b00816
- 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
- Ren Zhang, Bongjoon Lee, Michael R. Bockstaller, Sanat K. Kumar, Christopher M. Stafford, Jack F. Douglas, Dharmaraj Raghavan, and Alamgir Karim . Pattern-Directed Phase Separation of Polymer-Grafted Nanoparticles in a Homopolymer Matrix. Macromolecules 2016, 49 (10) , 3965-3974. https://doi.org/10.1021/acs.macromol.6b00228
- Saumil P. Samant, Christopher A. Grabowski, Kim Kisslinger, Kevin G. Yager, Guangcui Yuan, Sushil K. Satija, Michael F. Durstock, Dharmaraj Raghavan, and Alamgir Karim . Directed Self-Assembly of Block Copolymers for High Breakdown Strength Polymer Film Capacitors. ACS Applied Materials & Interfaces 2016, 8 (12) , 7966-7976. https://doi.org/10.1021/acsami.5b11851
- Itsuki Saito, Tsukasa Miyazaki, and Katsuhiro Yamamoto . Depth-Resolved Structure Analysis of Cylindrical Microdomain in Block Copolymer Thin Film by Grazing-Incidence Small-Angle X-ray Scattering Utilizing Low-Energy X-rays. Macromolecules 2015, 48 (22) , 8190-8196. https://doi.org/10.1021/acs.macromol.5b01883
- Wubin Bai, Karim Gadelrab, Alfredo Alexander-Katz, and Caroline A. Ross . Perpendicular Block Copolymer Microdomains in High Aspect Ratio Templates. Nano Letters 2015, 15 (10) , 6901-6908. https://doi.org/10.1021/acs.nanolett.5b02815
- Pawel W. Majewski and Kevin G. Yager . Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films. Nano Letters 2015, 15 (8) , 5221-5228. https://doi.org/10.1021/acs.nanolett.5b01463
- Raleigh L. Davis, Brian T. Michal, Paul M. Chaikin, and Richard A. Register . Progression of Alignment in Thin Films of Cylinder-Forming Block Copolymers upon Shearing. Macromolecules 2015, 48 (15) , 5339-5347. https://doi.org/10.1021/acs.macromol.5b01028
- Pawel W. Majewski and Kevin G. Yager . Block Copolymer Response to Photothermal Stress Fields. Macromolecules 2015, 48 (13) , 4591-4598. https://doi.org/10.1021/acs.macromol.5b00955
- Ming Luo, Douglas M. Scott, and Thomas H. Epps, III . Writing Highly Ordered Macroscopic Patterns in Cylindrical Block Polymer Thin Films via Raster Solvent Vapor Annealing and Soft Shear. ACS Macro Letters 2015, 4 (5) , 516-520. https://doi.org/10.1021/acsmacrolett.5b00126
- Pawel W. Majewski and Kevin G. Yager . Millisecond Ordering of Block Copolymer Films via Photothermal Gradients. ACS Nano 2015, 9 (4) , 3896-3906. https://doi.org/10.1021/nn5071827
- So Youn Kim, Adam Nunns, Jessica Gwyther, Raleigh L. Davis, Ian Manners, Paul M. Chaikin, and Richard A. Register . Large-Area Nanosquare Arrays from Shear-Aligned Block Copolymer Thin Films. Nano Letters 2014, 14 (10) , 5698-5705. https://doi.org/10.1021/nl502416b
- Hanqiong Hu, Jonathan P. Singer, and Chinedum O. Osuji . Morphology Development in Thin Films of a Lamellar Block Copolymer Deposited by Electrospray. Macromolecules 2014, 47 (16) , 5703-5710. https://doi.org/10.1021/ma500376n
- Arash Nikoubashman, Raleigh L. Davis, Brian T. Michal, Paul M. Chaikin, Richard A. Register, and Athanassios Z. Panagiotopoulos . Thin Films of Homopolymers and Cylinder-Forming Diblock Copolymers under Shear. ACS Nano 2014, 8 (8) , 8015-8026. https://doi.org/10.1021/nn502068e
- Raleigh L. Davis, Paul M. Chaikin, and Richard A. Register . Cylinder Orientation and Shear Alignment in Thin Films of Polystyrene–Poly(n-hexyl methacrylate) Diblock Copolymers. Macromolecules 2014, 47 (15) , 5277-5285. https://doi.org/10.1021/ma5012705
- Yu Wang, Wei-Hong Katie Zhong, Jianying Ji, and Allen Eyler . Blossoming of Nanosheet Structures via a Disturbed Self-Assembly. Nano Letters 2014, 14 (6) , 3474-3480. https://doi.org/10.1021/nl501002f
- Zhe Qiang, Longhe Zhang, Gila E. Stein, Kevin A. Cavicchi, and Bryan D. Vogt . Unidirectional Alignment of Block Copolymer Films Induced by Expansion of a Permeable Elastomer during Solvent Vapor Annealing. Macromolecules 2014, 47 (3) , 1109-1116. https://doi.org/10.1021/ma402131j
- Changhuai Ye, Gurpreet Singh, Maurice L. Wadley, Alamgir Karim, Kevin A. Cavicchi, and Bryan D. Vogt . Anisotropic Mechanical Properties of Aligned Polystyrene-block-polydimethylsiloxane Thin Films. Macromolecules 2013, 46 (21) , 8608-8615. https://doi.org/10.1021/ma401780r
- Ming Luo and Thomas H. Epps, III . Directed Block Copolymer Thin Film Self-Assembly: Emerging Trends in Nanopattern Fabrication. Macromolecules 2013, 46 (19) , 7567-7579. https://doi.org/10.1021/ma401112y
- Li Yao, Arthur R. Woll, and James J. Watkins . Directed Assembly of Block Copolymer Templates for the Fabrication of Mesoporous Silica Films with Controlled Architectures via 3-D Replication. Macromolecules 2013, 46 (15) , 6132-6144. https://doi.org/10.1021/ma401018y
- Gurpreet Singh, Saurabh Batra, Ren Zhang, Hongyi Yuan, Kevin G. Yager, Miko Cakmak, Brian Berry, and Alamgir Karim . Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films. ACS Nano 2013, 7 (6) , 5291-5299. https://doi.org/10.1021/nn401094s
- Brian C. Berry, Gurpreet Singh, Ho-Cheol Kim, and Alamgir Karim . Highly Aligned Block Copolymer Thin Films by Synergistic Coupling of Static Graphoepitaxy and Dynamic Thermal Annealing Fields. ACS Macro Letters 2013, 2 (4) , 346-350. https://doi.org/10.1021/mz400054y
- 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
- Hoang M. Nguyen, Ariane V. Mader, Swarnalok De, Jaana Vapaavuori. Understanding nanodomain morphology formation in dip-coated PS- b -PEO thin films. Nanoscale Advances 2021, 3 (17) , 4996-5007. https://doi.org/10.1039/D1NA00263E
- Saumil Samant, Shimelis Hailu, Maninderjeet Singh, Nihar Pradhan, Kevin Yager, Abdullah M. Al‐Enizi, Dharmaraj Raghavan, Alamgir Karim. Alignment frustration in block copolymer films with block copolymer grafted TiO 2 nanoparticles under soft‐shear cold zone annealing. Polymers for Advanced Technologies 2021, 32 (5) , 2052-2060. https://doi.org/10.1002/pat.5234
- Cédric Kilchoer, Doha Abdelrahman, S. Narjes Abdollahi, Ava A. LaRocca, Ullrich Steiner, Matthias Saba, Ilja Gunkel, Bodo D. Wilts. Hyperbolic Optical Metamaterials from Shear‐Aligned Block Copolymer Cylinder Arrays. Advanced Photonics Research 2020, 1 (2) , 2000037. https://doi.org/10.1002/adpr.202000037
- Yan Luo, Xiaoteng Wang, Ren Zhang, Maninderjeet Singh, Ali Ammar, Diana Cousins, Mohammad K. Hassan, Deepalekshmi Ponnamma, Samer Adham, Mariam Al Ali Al-Maadeed, Alamgir Karim. Vertically oriented nanoporous block copolymer membranes for oil/water separation and filtration. Soft Matter 2020, 16 (42) , 9648-9654. https://doi.org/10.1039/D0SM00526F
- Juanjuan Wang, Weihe Shi, Zhengjie Luo, Shuangjun Chen, Kailai Xue. Reversible polystyrene-block-poly(methyl methacrylate) copolymer films with perpendicular orientation by ultra-thin polystyrene substrates. Progress in Organic Coatings 2020, 147 , 105721. https://doi.org/10.1016/j.porgcoat.2020.105721
- Le Dai, Hui Cao, Hai Deng. Highly Ordered Methacrylate Block Copolymers Containing Liquid Crystal Side Chains. Journal of Photopolymer Science and Technology 2020, 33 (5) , 541-544. https://doi.org/10.2494/photopolymer.33.541
- Samantha R. Nowak, Kevin G. Yager. Photothermally Directed Assembly of Block Copolymers. Advanced Materials Interfaces 2020, 7 (5) , 1901679. https://doi.org/10.1002/admi.201901679
- Timothy D. Yee, Carla L. Watson, John D. Roehling, T. Yong-Jin Han, Anna M. Hiszpanski. Fabrication and 3D tomographic characterization of nanowire arrays and meshes with tunable dimensions from shear-aligned block copolymers. Soft Matter 2019, 15 (24) , 4898-4904. https://doi.org/10.1039/C9SM00303G
- 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
- Tianxing Ma, Jennifer Guzman-Pichardo, Lisa Klein, Andrei Jitianu, Jonathan P. Singer, , , . Focused laser spike (FLaSk) thermocapillary patterning of micro/nanostructures. 2019,,, 39. https://doi.org/10.1117/12.2507662
- Eduardo Fernandez, Kun-Hua Tu, Pin Ho, Caroline A Ross. Thermal stability of L1 0 -FePt nanodots patterned by self-assembled block copolymer lithography. Nanotechnology 2018, 29 (46) , 465301. https://doi.org/10.1088/1361-6528/aade2f
- A. S. Merekalov, Y. I. Derikov, A. A. Ezhov, E. N. Govorun, Y. V. Kudryavtsev. Evolution of Microstructure in Block Copolymer Thin Films during Zone Annealing. Polymer Science, Series A 2018, 60 (6) , 723-733. https://doi.org/10.1134/S0965545X18060068
- Giang Thi Vu, Anabella A. Abate, Leopoldo R. Gómez, Aldo D. Pezzutti, Richard A. Register, Daniel A. Vega, Friederike Schmid. Curvature as a Guiding Field for Patterns in Thin Block Copolymer Films. Physical Review Letters 2018, 121 (8) https://doi.org/10.1103/PhysRevLett.121.087801
- Jing Zhao, Chen Lu, Shuo Guo, Ke Wang, Qiang Fu. Polymorphic structures phase diagram of shear-induced isotactic polypropylene/carbon fiber cylindrites. Materials & Design 2018, 150 , 40-48. https://doi.org/10.1016/j.matdes.2018.04.030
- Mohan Raj Krishnan, Kai-Yuan Lu, Wen-Yu Chiu, I-Chen Chen, Jheng-Wei Lin, Ting-Ya Lo, Prokopios Georgopanos, Apostolos Avgeropoulos, Ming-Chang Lee, Rong-Ming Ho. Directed Self-Assembly of Star-Block Copolymers by Topographic Nanopatterns through Nucleation and Growth Mechanism. Small 2018, 14 (16) , 1704005. https://doi.org/10.1002/smll.201704005
- Ting-Ya Lo, Mohan Raj Krishnan, Kai-Yuan Lu, Rong-Ming Ho. Silicon-containing block copolymers for lithographic applications. Progress in Polymer Science 2018, 77 , 19-68. https://doi.org/10.1016/j.progpolymsci.2017.10.002
- 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
- Joseph D. Hill, Paul C. Millett. Numerical Simulations of Directed Self-Assembly in Diblock Copolymer Films using Zone Annealing and Pattern Templating. Scientific Reports 2017, 7 (1) https://doi.org/10.1038/s41598-017-05565-w
- 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
- 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
- Yuyan Gao, Huanyu Cheng. Assembly of Heterogeneous Materials for Biology and Electronics: From Bio-Inspiration to Bio-Integration. Journal of Electronic Packaging 2017, 139 (2) https://doi.org/10.1115/1.4036238
- Ren Zhang, Bongjoon Lee, Christopher M. Stafford, Jack F. Douglas, Andrey V. Dobrynin, Michael R. Bockstaller, Alamgir Karim. Entropy-driven segregation of polymer-grafted nanoparticles under confinement. Proceedings of the National Academy of Sciences 2017, 114 (10) , 2462-2467. https://doi.org/10.1073/pnas.1613828114
- Melody A. Morris, Thomas E. Gartner, Thomas H. Epps. Tuning Block Polymer Structure, Properties, and Processability for the Design of Efficient Nanostructured Materials Systems. Macromolecular Chemistry and Physics 2017, 218 (5) , 1600513. https://doi.org/10.1002/macp.201600513
- 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
- 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
- Charles T. Black, Christopher Forrey, Kevin G. Yager. Thickness-dependence of block copolymer coarsening kinetics. Soft Matter 2017, 13 (18) , 3275-3283. https://doi.org/10.1039/C7SM00212B
- 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
- Itsuki Saito, Daiki Shimada, Mayu Aikawa, Tsukasa Miyazaki, Keisuke Shimokita, Hideaki Takagi, Katsuhiro Yamamoto. Orientation and relaxation behaviors of lamellar microdomains of poly(methyl methacrylate)-b-poly(n-butyl acrylate) thin films as revealed by grazing-incidence small-angle X-ray scattering. Polymer Journal 2016, 48 (4) , 399-406. https://doi.org/10.1038/pj.2016.2
- Zhinan Cong, Liangshun Zhang, Liquan Wang, Jiaping Lin. Understanding the ordering mechanisms of self-assembled nanostructures of block copolymers during zone annealing. The Journal of Chemical Physics 2016, 144 (11) , 114901. https://doi.org/10.1063/1.4943864
- W. Bai, C.A. Ross. Functional nanostructured materials based on self-assembly of block copolymers. MRS Bulletin 2016, 41 (2) , 100-107. https://doi.org/10.1557/mrs.2016.1
- Ren Zhang, Bongjoon Lee, Michael R. Bockstaller, Abdullah M. Al-Enizi, Ahmed Elzatahry, Brian C. Berry, Alamgir Karim. Soft-shear induced phase-separated nanoparticle string-structures in polymer thin films. Faraday Discussions 2016, 186 , 31-43. https://doi.org/10.1039/C5FD00141B
- Ting Qu, Yongbin Zhao, Zongbo Li, Pingping Wang, Shubo Cao, Yawei Xu, Yayuan Li, Aihua Chen. Micropore extrusion-induced alignment transition from perpendicular to parallel of cylindrical domains in block copolymers. Nanoscale 2016, 8 (6) , 3268-3273. https://doi.org/10.1039/C5NR09140C
- Zhiqiang Wu, Gang Wang, Mengwei Zhang, Ke Wang, Qiang Fu. Facilely assess the soluble behaviour of the β-nucleating agent by gradient temperature field for the construction of heterogeneous crystalline-frameworks in iPP. Soft Matter 2016, 12 (2) , 594-601. https://doi.org/10.1039/C5SM02030A
- Xiaoxiong Zheng, Zongbo Li, Yongbin Zhao, Ting Qu, Shubo Cao, Pingping Wang, Yayuan Li, Tomokazu Iyoda, Aihua Chen. Polydimethylsiloxane-assisted alignment transition from perpendicular to parallel of cylindrical microdomains in block copolymer films. RSC Advances 2016, 6 (96) , 93298-93302. https://doi.org/10.1039/C6RA21165H
- Abul F. Huq, Manish Kulkarni, Arvind Modi, Detlef-M. Smilgies, Abdullah M. Al-Enizi, Ahmed Elzatahry, Dharmaraj Raghavan, Alamgir Karim. Vertical orientation of solvent cast nanofilled PS-b-PEO block copolymer thin films at high nanoparticle loading. Polymer 2016, 82 , 22-31. https://doi.org/10.1016/j.polymer.2015.10.049
- Pawel W. Majewski, Atikur Rahman, Charles T. Black, Kevin G. Yager. Arbitrary lattice symmetries via block copolymer nanomeshes. Nature Communications 2015, 6 (1) https://doi.org/10.1038/ncomms8448
- Sang-Woo Kim, Eunhye Kim, Hoyeon Lee, Brian C. Berry, Ho-Cheol Kim, Du Yeol Ryu. Thickness-dependent ordering of perpendicularly oriented lamellae in PS-b-PMMA thin films. Polymer 2015, 74 , 63-69. https://doi.org/10.1016/j.polymer.2015.07.053
- Zhe Qiang, Maurice L. Wadley, Bryan D. Vogt, Kevin A. Cavicchi. Facile non-lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene- block -polydimethylsiloxane films. Journal of Polymer Science Part B: Polymer Physics 2015, 53 (15) , 1058-1064. https://doi.org/10.1002/polb.23740
- Takejiro Inoue, Dustin W. Janes, Jiaxing Ren, Hyo Seon Suh, Xuanxuan Chen, Christopher J. Ellison, Paul F. Nealey. Molecular Transfer Printing of Block Copolymer Patterns over Large Areas with Conformal Layers. Advanced Materials Interfaces 2015, 2 (10) , 1500133. https://doi.org/10.1002/admi.201500133
- Jiyoung Jeong, Jeong Sook Ha, Sang-Soo Lee, Jeong Gon Son. Topcoat-Assisted Perpendicular and Straightly Parallel Coexisting Orientations of Block Copolymer Films. Macromolecular Rapid Communications 2015, 36 (13) , 1261-1266. https://doi.org/10.1002/marc.201500088
- Qiangli Zhao, Yancong Feng, Chen Zhang, Zhongjie Du, Ming Tian, Jianguo Mi. Extension of integral equation theory to microphase separation of block copolymers. Molecular Physics 2015, 113 (8) , 880-889. https://doi.org/10.1080/00268976.2014.985754
- Saumil Samant, Shimelis T. Hailu, Abdullah M. Al‐Enizi, Alamgir Karim, Dharmaraj Raghavan. Orientation control in nanoparticle filled block copolymer cold zone annealed films. Journal of Polymer Science Part B: Polymer Physics 2015, 53 (8) , 604-614. https://doi.org/10.1002/polb.23684
- Eunkyoung Yoon, Eunjin Kim, Daeheum Kim, Jeong Gon Son. Top-Coat Dewetting for the Highly Ordered Lateral Alignment of Block Copolymer Microdomains in Thin Films. Advanced Functional Materials 2015, 25 (6) , 913-919. https://doi.org/10.1002/adfm.201403046
- Biswajit Sarkar, Paschalis Alexandridis. Block copolymer–nanoparticle composites: Structure, functional properties, and processing. Progress in Polymer Science 2015, 40 , 33-62. https://doi.org/10.1016/j.progpolymsci.2014.10.009
- Xiaohua Zhang, Jack F. Douglas, Sushil Satija, Alamgir Karim. Enhanced vertical ordering of block copolymer films by tuning molecular mass. RSC Advances 2015, 5 (41) , 32307-32318. https://doi.org/10.1039/C5RA02047F
- Kevin G. Yager, Christopher Forrey, Gurpreet Singh, Sushil K. Satija, Kirt A. Page, Derek L. Patton, Jack F. Douglas, Ronald L. Jones, Alamgir Karim. Thermally-induced transition of lamellae orientation in block-copolymer films on ‘neutral’ nanoparticle-coated substrates. Soft Matter 2015, 11 (25) , 5154-5167. https://doi.org/10.1039/C5SM00896D
- Gregory S. Doerk, Joy Y. Cheng, Gurpreet Singh, Charles T. Rettner, Jed W. Pitera, Srinivasan Balakrishnan, Noel Arellano, Daniel P. Sanders. Enabling complex nanoscale pattern customization using directed self-assembly. Nature Communications 2014, 5 (1) https://doi.org/10.1038/ncomms6805
- Robert D. Peters, Kari Dalnoki-Veress. Strain rate effects on symmetric diblock copolymer liquid bridges: Order-induced stability of polymer fibres. The European Physical Journal E 2014, 37 (10) https://doi.org/10.1140/epje/i2014-14100-8
- Jonathan R. Felts, M. Serdar Onses, John A. Rogers, William P. King. Nanometer Scale Alignment of Block-Copolymer Domains by Means of a Scanning Probe Tip. Advanced Materials 2014, 26 (19) , 2999-3002. https://doi.org/10.1002/adma.201305481
- Joseph Kao, Seong-Jun Jeong, Zhang Jiang, Dong Hyun Lee, Karim Aissou, Caroline A. Ross, Thomas P. Russell, Ting Xu. Direct 3-D Nanoparticle Assemblies in Thin Films via Topographically Patterned Surfaces. Advanced Materials 2014, 26 (18) , 2777-2781. https://doi.org/10.1002/adma.201305561
- Jonathan P. Singer, Kevin W. Gotrik, Jae-Hwang Lee, Steven E. Kooi, Caroline A. Ross, Edwin L. Thomas. Alignment and reordering of a block copolymer by solvent-enhanced thermal laser direct write. Polymer 2014, 55 (7) , 1875-1882. https://doi.org/10.1016/j.polymer.2014.02.028
- Nicolas Goubet, Marie-Paule Pileni. Negative supracrystals inducing a FCC-BCC transition in gold nanocrystal superlattices. Nano Research 2014, 7 (2) , 171-179. https://doi.org/10.1007/s12274-013-0384-9
- Manesh Gopinadhan, Chinedum O. Osuji. Domain Orientation in Bulk Block Copolymers. 2014,,, 1-10. https://doi.org/10.1007/978-3-642-36199-9_81-1
- Zhe Qiang, Yuanzhong Zhang, Jesse A. Groff, Kevin A. Cavicchi, Bryan D. Vogt. A generalized method for alignment of block copolymer films: solvent vapor annealing with soft shear. Soft Matter 2014, 10 (32) , 6068-6076. https://doi.org/10.1039/C4SM00875H
- Hanqiong Hu, Manesh Gopinadhan, Chinedum O. Osuji. Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter. Soft Matter 2014, 10 (22) , 3867. https://doi.org/10.1039/c3sm52607k
- Ren Zhang, Gurpreet Singh, Alei Dang, Lu Dai, Michael R. Bockstaller, Bulent Akgun, Sushil Satija, Alamgir Karim. Nanoparticle-Driven Orientation Transition and Soft-Shear Alignment in Diblock Copolymer Films via Dynamic Thermal Gradient Field. Macromolecular Rapid Communications 2013, 34 (20) , 1642-1647. https://doi.org/10.1002/marc.201300485
- Jiachen Xue, Gurpreet Singh, Zhe Qiang, Alamgir Karim, Bryan D. Vogt. Unidirectional self-assembly of soft templated mesoporous carbons by zone annealing. Nanoscale 2013, 5 (17) , 7928. https://doi.org/10.1039/c3nr02821f



