On-Demand Selection of the Latent Domain Orientation in Spray-Deposited Block Copolymer Thin Films

Cetindag, Semih; Bellini, Beatrice; Li, Ruipeng; Tsai, Esther H.R.; Nykypanchuk, Dmytro; Doerk, Gregory S.

doi:10.1021/acsnano.4c14499

Title: On-Demand Selection of the Latent Domain Orientation in Spray-Deposited Block Copolymer Thin Films

Journal Article · 09 January 2025 · ACS Nano

DOI: https://doi.org/10.1021/acsnano.4c14499 · OSTI ID:2506716

Cetindag, Semih ^[1]; Bellini, Beatrice ^[2]; Li, Ruipeng ^[3]; Tsai, Esther H.R. ^[1]; Nykypanchuk, Dmytro ^[1];

^[1]

Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Columbia Univ., New York, NY (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

With their ability to self-assemble spontaneously into well-defined nanoscale morphologies, block copolymer (BCP) thin films are a versatile platform to fabricate functional nanomaterials. An important challenge to wider deployment of BCPs in nanofabrication is combining precise control over the nanoscale domain orientation in BCP assemblies with scalable deposition techniques that are applicable to large-area, curved, and flexible substrates. Here, in this study, we show that spray-deposited smooth films of a nominally disordered BCP exhibit latent orientations, which can be prescriptively selected by controlling solvent evaporation during spray casting. Subsequent solvent vapor annealing triggers assembly toward highly ordered cylindrical morphologies along the pathway determined by solvent evaporation in the prior spray deposition stage. Faster evaporation promotes assembly of vertically oriented cylinders spanning the entire film thickness (100–300 nm). In comparison, slow solvent evaporation permits intermicellar aggregation and incipient cylinder formation in solution, which induces horizontal cylinder assembly upon annealing. The evaporatively controlled latent orientation mechanism presented herein elucidates how nonequilibrium phenomena during casting govern successive self-assembly pathways and facilitates a versatile method to dictate the domain orientation of BCP thin films on demand on flexible and highly curved substrates or in distinct pattern areas on the same substrate.

View Accepted Manuscript (DOE)

Cite

Export

Save

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2506716

Report Number(s):: BNL--227521-2025-JAAM

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 3 Vol. 19; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (72)

A Top Coat with Solvent Annealing Enables Perpendicular Orientation of Sub-10 nm Microdomains in Si-Containing Block Copolymer Thin Films Kim, Eunjin; Kim, Wonjung; Lee, Kwang Hee Advanced Functional Materials, Vol. 24, Issue 44 https://doi.org/10.1002/adfm.201401678	journal	September 2014
Fabrication of Nanoporous Alumina Ultrafiltration Membrane with Tunable Pore Size Using Block Copolymer Templates Zhou, Chun; Segal-Peretz, Tamar; Oruc, Muhammed Enes Advanced Functional Materials, Vol. 27, Issue 34 https://doi.org/10.1002/adfm.201701756	journal	July 2017
Spray‐Coated Colloidal Perovskite Quantum Dot Films for Highly Efficient Solar Cells Yuan, Jifeng; Bi, Chenghao; Wang, Shixun Advanced Functional Materials, Vol. 29, Issue 49 https://doi.org/10.1002/adfm.201906615	journal	September 2019
Integration of Polymer Synthesis and Self‐Assembly for Controlled Periodicity and Photonic Properties Zhang, Ruimeng; Qiang, Zhe; Wang, Muzhou Advanced Functional Materials, Vol. 31, Issue 1 https://doi.org/10.1002/adfm.202005819	journal	September 2020
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
Macroscopic Orientation of Block Copolymer Cylinders in Single-Layer Films by Shearing Angelescu, D. E.; Waller, J. H.; Adamson, D. H. Advanced Materials, Vol. 16, Issue 19 https://doi.org/10.1002/adma.200400643	journal	October 2004
Tuning Solute‐Redistribution Dynamics for Scalable Fabrication of Colloidal Quantum‐Dot Optoelectronics Choi, Min‐Jae; Kim, YongJoo; Lim, Hunhee Advanced Materials https://doi.org/10.1002/adma.201805886	journal	May 2019
Understanding Film Thickness‐Dependent Block Copolymer Self‐Assembly by Controlled Polymer Dewetting on Prepatterned Surfaces Brassat, Katharina; Kool, Daniel; Nallet, Colin G. A. Advanced Materials Interfaces, Vol. 7, Issue 1 https://doi.org/10.1002/admi.201901605	journal	November 2019
Block Copolymer Directed Metamaterials and Metasurfaces for Novel Optical Devices Alvarez‐Fernandez, Alberto; Cummins, Cian; Saba, Matthias Advanced Optical Materials, Vol. 9, Issue 16 https://doi.org/10.1002/adom.202100175	journal	May 2021
Physical Continuity and Vertical Alignment of Block Copolymer Domains by Kinetically Controlled Electrospray Deposition Hu, Hanqiong; Choo, Youngwoo; Feng, Xunda Macromolecular Rapid Communications, Vol. 36, Issue 13 https://doi.org/10.1002/marc.201500099	journal	May 2015
Current spray-coating approaches to manufacture perovskite solar cells Alanazi, Tarek I. Results in Physics, Vol. 44 https://doi.org/10.1016/j.rinp.2022.106144	journal	January 2023
Advances in Spray-Cast Perovskite Solar Cells Bishop, James E.; Routledge, Thomas J.; Lidzey, David G. The Journal of Physical Chemistry Letters, Vol. 9, Issue 8 https://doi.org/10.1021/acs.jpclett.8b00311	journal	April 2018
Film Thickness and Composition Effects in Symmetric Ternary Block Copolymer/Homopolymer Blend Films: Domain Spacing and Orientation Toth, Kristof; Bae, Suwon; Osuji, Chinedum O. Macromolecules, Vol. 54, Issue 17 https://doi.org/10.1021/acs.macromol.1c01032	journal	August 2021
Simulation of Solvent Evaporation from a Diblock Copolymer Film: Orientation of the Cylindrical Mesophase Dreyer, Oliver; Ibbeken, Gregor; Schneider, Ludwig Macromolecules, Vol. 55, Issue 17 https://doi.org/10.1021/acs.macromol.2c00612	journal	August 2022
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
Self-Assembly in Block Copolymer Thin Films upon Solvent Evaporation: A Simulation Study Hao, Jinlong; Wang, Zhan; Wang, Zheng Macromolecules, Vol. 50, Issue 11 https://doi.org/10.1021/acs.macromol.7b00200	journal	May 2017
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
Roll-to-Roll Scalable Production of Ordered Microdomains through Nonvolatile Additive Solvent Annealing of Block Copolymers Weller, Daniel W.; Galuska, Luke; Wang, Weiyu Macromolecules, Vol. 52, Issue 13 https://doi.org/10.1021/acs.macromol.9b00772	journal	June 2019
Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly Doerk, Gregory S.; Li, Ruipeng; Fukuto, Masafumi Macromolecules, Vol. 53, Issue 3 https://doi.org/10.1021/acs.macromol.9b02296	journal	January 2020
Latent Alignment in Pathway-Dependent Ordering of Block Copolymer Thin Films Majewski, Pawel W.; Yager, Kevin G. Nano Letters, Vol. 15, Issue 8 https://doi.org/10.1021/acs.nanolett.5b01463	journal	July 2015
Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns Kulkarni, Ashish A.; Doerk, Gregory S. ACS Applied Materials & Interfaces, Vol. 14, Issue 23 https://doi.org/10.1021/acsami.2c05911	journal	June 2022
Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates Bellini, Beatrice; Willard, Jasmine R.; Cetindag, Semih ACS Applied Materials & Interfaces, Vol. 16, Issue 27 https://doi.org/10.1021/acsami.4c05715	journal	June 2024
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
From Lab to Fab: Enabling Enhanced Control of Block Polymer Thin-Film Nanostructures Gottlieb, Eric R.; Guliyeva, Aynur; Epps, Thomas H. ACS Applied Polymer Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsapm.1c00680	journal	August 2021
Macroscopic Alignment of Block Copolymers on Silicon Substrates by Laser Annealing Leniart, Arkadiusz A.; Pula, Przemyslaw; Sitkiewicz, Andrzej ACS Nano, Vol. 14, Issue 4 https://doi.org/10.1021/acsnano.0c00696	journal	March 2020
Next-Generation Ultrafiltration Membranes Enabled by Block Polymers Hampu, Nicholas; Werber, Jay R.; Chan, Wui Yarn ACS Nano, Vol. 14, Issue 12 https://doi.org/10.1021/acsnano.0c07883	journal	December 2020
Shear-Rolling Process for Unidirectionally and Perpendicularly Oriented Sub-10-nm Block Copolymer Patterns on the 4 in Scale Oh, Jinwoo; Shin, Minkyung; Kim, In Soo ACS Nano, Vol. 15, Issue 5 https://doi.org/10.1021/acsnano.1c00358	journal	May 2021
Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends Doerk, Gregory S.; Yager, Kevin G. ACS Nano, Vol. 11, Issue 12 https://doi.org/10.1021/acsnano.7b06154	journal	October 2016
Solvent Annealed Thin Films of Asymmetric Polyisoprene−Polylactide Diblock Copolymers Cavicchi, Kevin A.; Russell, Thomas P. Macromolecules, Vol. 40, Issue 4 https://doi.org/10.1021/ma061163w	journal	February 2007
Cylinder Orientation Mechanism in Block Copolymer Thin Films Upon Solvent Evaporation Phillip, William A.; Hillmyer, Marc A.; Cussler, E. L. Macromolecules, Vol. 43, Issue 18 https://doi.org/10.1021/ma1012946	journal	September 2010
Morphology Development in Thin Films of a Lamellar Block Copolymer Deposited by Electrospray Hu, Hanqiong; Singer, Jonathan P.; Osuji, Chinedum O. Macromolecules, Vol. 47, Issue 16 https://doi.org/10.1021/ma500376n	journal	August 2014
Morphological Development in Solvent-Cast Polystyrene−Polybutadiene−Polystyrene (SBS) Triblock Copolymer Thin Films Kim, G.; Libera, M. Macromolecules, Vol. 31, Issue 8 https://doi.org/10.1021/ma971349i	journal	April 1998
Block Copolymer Self Assembly during Rapid Solvent Evaporation: Insights into Cylinder Growth and Stability Paradiso, Sean P.; Delaney, Kris T.; García-Cervera, Carlos J. ACS Macro Letters, Vol. 3, Issue 1 https://doi.org/10.1021/mz400572r	journal	December 2013
Long-Range Ordering of Block Copolymer Cylinders Driven by Combining Thermal Annealing and Substrate Functionalization She, Ming-Shiuan; Lo, Ting-Ya; Ho, Rong-Ming ACS Nano, Vol. 7, Issue 3 https://doi.org/10.1021/nn305725q	journal	March 2013
Continuous Equilibrated Growth of Ordered Block Copolymer Thin Films by Electrospray Deposition Hu, Hanqiong; Rangou, Sofia; Kim, Myungwoong ACS Nano, Vol. 7, Issue 4 https://doi.org/10.1021/nn400279a	journal	March 2013
Large-Scale Roll-to-Roll Fabrication of Vertically Oriented Block Copolymer Thin Films Singh, Gurpreet; Batra, Saurabh; Zhang, Ren ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn401094s	journal	May 2013
Monoliths of Semiconducting Block Copolymers by Magnetic Alignment Tran, Helen; Gopinadhan, Manesh; Majewski, Pawel W. ACS Nano, Vol. 7, Issue 6 https://doi.org/10.1021/nn401725a	journal	May 2013
Two-Dimensional Pattern Formation Using Graphoepitaxy of PS- b -PMMA Block Copolymers for Advanced FinFET Device and Circuit Fabrication Tsai, Hsinyu; Pitera, Jed W.; Miyazoe, Hiroyuki ACS Nano, Vol. 8, Issue 5 https://doi.org/10.1021/nn501300b	journal	April 2014
Thin Films of Homopolymers and Cylinder-Forming Diblock Copolymers under Shear Nikoubashman, Arash; Davis, Raleigh L.; Michal, Brian T. ACS Nano, Vol. 8, Issue 8 https://doi.org/10.1021/nn502068e	journal	July 2014
Scalable Fabrication of Polymer Membranes with Vertically Aligned 1 nm Pores by Magnetic Field Directed Self-Assembly Feng, Xunda; Tousley, Marissa E.; Cowan, Matthew G. ACS Nano, Vol. 8, Issue 12 https://doi.org/10.1021/nn505037b	journal	November 2014
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
Electric Field Alignment of a Block Copolymer Nanopattern: Direct Observation of the Microscopic Mechanism Olszowka, Violetta; Hund, Markus; Kuntermann, Volker ACS Nano, Vol. 3, Issue 5 https://doi.org/10.1021/nn900081u	journal	April 2009
Molecular Transfer Printing Using Block Copolymers Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang ACS Nano, Vol. 4, Issue 2 https://doi.org/10.1021/nn901342j	journal	December 2009
Capillary flow as the cause of ring stains from dried liquid drops Deegan, Robert D.; Bakajin, Olgica; Dupont, Todd F. Nature, Vol. 389, Issue 6653, p. 827-829 https://doi.org/10.1038/39827	journal	October 1997
Highly tunable refractive index visible-light metasurface from block copolymer self-assembly Kim, Ju Young; Kim, Hyowook; Kim, Bong Hoon Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12911	journal	September 2016
Self-assembled hydrogels utilizing polymer–nanoparticle interactions Appel, Eric A.; Tibbitt, Mark W.; Webber, Matthew J. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7295	journal	February 2015
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
Universal perpendicular orientation of block copolymer microdomains using a filtered plasma Oh, Jinwoo; Suh, Hyo Seon; Ko, Youngpyo Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-10907-5	journal	July 2019
Priming self-assembly pathways by stacking block copolymers Russell, Sebastian T.; Bae, Suwon; Subramanian, Ashwanth Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-34729-0	journal	November 2022
Efficient electrospray deposition of surfaces smaller than the spray plume Park, Sarah H.; Lei, Lin; D’Souza, Darrel Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-40638-7	journal	August 2023
Hierarchically engineered nanostructures from compositionally anisotropic molecular building blocks Liang, Ruiqi; Xue, Yazhen; Fu, Xiaowei Nature Materials, Vol. 21, Issue 12 https://doi.org/10.1038/s41563-022-01393-0	journal	November 2022
Unravelling inherent electrocatalysis of mixed-conducting oxide activated by metal nanoparticle for fuel cell electrodes Choi, Yoonseok; Cha, Seung Keun; Ha, Hyunwoo Nature Nanotechnology, Vol. 14, Issue 3 https://doi.org/10.1038/s41565-019-0367-4	journal	February 2019
Emergence of layered nanoscale mesh networks through intrinsic molecular confinement self-assembly Sun, Zehao; Liu, Runze; Su, Tingyu Nature Nanotechnology, Vol. 18, Issue 3 https://doi.org/10.1038/s41565-022-01293-z	journal	January 2023
Macroscopic materials assembled from nanoparticle superlattices Santos, Peter J.; Gabrys, Paul A.; Zornberg, Leonardo Z. Nature, Vol. 591, Issue 7851 https://doi.org/10.1038/s41586-021-03355-z	journal	March 2021
A generalized method for alignment of block copolymer films: solvent vapor annealing with soft shear Qiang, Zhe; Zhang, Yuanzhong; Groff, Jesse A. Soft Matter, Vol. 10, Issue 32 https://doi.org/10.1039/C4SM00875H	journal	January 2014
Reordering transitions during annealing of block copolymer cylinder phases Majewski, Pawel W.; Yager, Kevin G. Soft Matter, Vol. 12, Issue 1 https://doi.org/10.1039/C5SM02441B	journal	January 2016
Determination of the maximum thickness for directed self-assembly of cylinder-forming PS-b-PMMA films on chemical patterns Liu, Yadong; Ji, Shengxiang Molecular Systems Design & Engineering, Vol. 3, Issue 2 https://doi.org/10.1039/C7ME00101K	journal	January 2018
Three-dimensional electroactive ZnO nanomesh directly derived from hierarchically self-assembled block copolymer thin films Subramanian, Ashwanth; Doerk, Gregory; Kisslinger, Kim Nanoscale, Vol. 11, Issue 19 https://doi.org/10.1039/C9NR00206E	journal	January 2019
High-throughput morphology mapping of self-assembling ternary polymer blends Toth, Kristof; Osuji, Chinedum O.; Yager, Kevin G. RSC Advances, Vol. 10, Issue 69 https://doi.org/10.1039/D0RA08491C	journal	January 2020
Solvent-assisted self-assembly of block copolymer thin films Pula, Przemyslaw; Leniart, Arkadiusz; Majewski, Pawel W. Soft Matter, Vol. 18, Issue 21 https://doi.org/10.1039/D2SM00439A	journal	January 2022
Influence of film casting method on block copolymer ordering in thin films Zhang, Xiaohua; Douglas, Jack F.; Jones, Ronald L. Soft Matter, Vol. 8, Issue 18 https://doi.org/10.1039/c2sm07308k	journal	January 2012
Confined thin film diblock copolymer in the presence of an electric field Ashok, B.; Muthukumar, M.; Russell, T. P. The Journal of Chemical Physics, Vol. 115, Issue 3 https://doi.org/10.1063/1.1380710	journal	July 2001
Self-assembled nanotextures impart broadband transparency to glass windows and solar cell encapsulants Liapis, Andreas C.; Rahman, Atikur; Black, Charles T. Applied Physics Letters, Vol. 111, Issue 18 https://doi.org/10.1063/1.5000965	journal	October 2017
Controlling orientational order in block copolymers using low-intensity magnetic fields Gopinadhan, Manesh; Choo, Youngwoo; Kawabata, Kohsuke Proceedings of the National Academy of Sciences, Vol. 114, Issue 45 https://doi.org/10.1073/pnas.1712631114	journal	October 2017
Catalyst design by scanning probe block copolymer lithography Huang, Liliang; Chen, Peng-Cheng; Liu, Mohan Proceedings of the National Academy of Sciences, Vol. 115, Issue 15 https://doi.org/10.1073/pnas.1800884115	journal	March 2018
Magnetic Alignment of Block Copolymer Microdomains by Intrinsic Chain Anisotropy Rokhlenko, Yekaterina; Gopinadhan, Manesh; Osuji, Chinedum O. Physical Review Letters, Vol. 115, Issue 25 https://doi.org/10.1103/PhysRevLett.115.258302	journal	December 2015
Ring to Mountain Transition in Deposition Pattern of Drying Droplets Man, Xingkun; Doi, Masao Physical Review Letters, Vol. 116, Issue 6 https://doi.org/10.1103/PhysRevLett.116.066101	journal	February 2016
Ultrasonic Atomization of Liquids Lang, Robert J. The Journal of the Acoustical Society of America, Vol. 34, Issue 1 https://doi.org/10.1121/1.1909020	journal	January 1962
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
Polarity-Switching Top Coats Enable Orientation of Sub-10-nm Block Copolymer Domains Bates, C. M.; Seshimo, T.; Maher, M. J. Science, Vol. 338, Issue 6108 https://doi.org/10.1126/science.1226046	journal	November 2012
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
Chameleon-like elastomers with molecularly encoded strain-adaptive stiffening and coloration Vatankhah-Varnosfaderani, Mohammad; Keith, Andrew N.; Cong, Yidan Science, Vol. 359, Issue 6383 https://doi.org/10.1126/science.aar5308	journal	March 2018

Similar Records

Self-Assembly of Supramolecular Thin Films: Role of Small Molecule and Solvent Vapor Annealing

Journal Article · 2018 · Macromolecules · OSTI ID:1504980

Evans, Katherine; Xu, Ting

Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer

Journal Article · 2016 · Macromolecules · OSTI ID:1351371

Choi, Jonathan W.; Carter, Matthew C. D.; Wei, Wei; +5 more

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

Journal Article · 2016 · Macromolecules · OSTI ID:1337643

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

Related Subjects

36 MATERIALS SCIENCE
Nanofabrication
block copolymer thin films
domain orientation
droplet evaporation
morphology
spray deposition

Title: On-Demand Selection of the Latent Domain Orientation in Spray-Deposited Block Copolymer Thin Films

Citation Formats

References (72)

Similar Records

Related Subjects