Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Hu, Mingqiu; Li, Xindi; Rzayev, Javid; Russell, Thomas P.

doi:10.1021/acs.macromol.3c02520

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Journal Article · Fri Feb 02 00:00:00 EST 2024 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c02520· OSTI ID:2429594

^[1]; Li, Xindi ^[2]; ^[2]; ^[3]

Univ. of Massachusetts, Amherst, MA (United States)
State Univ. of New York (SUNY), Buffalo, NY (United States)
Univ. of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

The self-assembly of high-χ low-N block copolymers (BCPs) can give patterns with sub-10 nm full pitch, serving as a promising alternative to photolithographic methods. Here, in this work, we synthesized poly(solketal methacrylate)-block-polystyrene copolymers, PSM-b-PS, with various volume ratios of the two blocks. After hydrolysis of the PSM block into poly(glycerol monomethacrylate), PGM, the BCPs had both lamellar and cylindrical microdomain morphologies in the bulk phase and in thin films. In addition to our previously developed solid-state hydrolysis strategy involving trifluoroacetic acid vapor, we developed a new photoinduced solid-state hydrolysis using photoacid generators, PAGs, embedded within the polymer films. After exposure to UV followed by a postexposure baking or solvent vapor annealing, the BCPs transitioned from the disordered, phase-mixed state into laterally ordered cylindrical patterns. In comparison to linear BCPs that rely on a random copolymer layer to modify interfacial interactions with the substrate to promote an orientation of the microdomains normal to the interface, we found that the microdomains in bottlebrush multiblock copolymers oriented normal to the interface absent substrate modification due to the chain architecture.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 2429594

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 3 Vol. 57; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns Bang, Joona; Jeong, Unyong; Ryu, Du Yeol Advanced Materials, Vol. 21, Issue 47, p. 4769-4792 https://doi.org/10.1002/adma.200803302	journal	July 2009
Patterning and Templating for Nanoelectronics Galatsis, Kosmas; Wang, Kang L.; Ozkan, Mihri Advanced Materials, Vol. 22, Issue 6 https://doi.org/10.1002/adma.200901689	journal	February 2010
In Situ Hydrolysis of Block Copolymers at the Water‐Oil Interface Chen, Zhan; Hu, Mingqiu; Li, Xindi Angewandte Chemie International Edition, Vol. 61, Issue 25 https://doi.org/10.1002/anie.202201392	journal	April 2022
Thermal Approaches to Perpendicular Block Copolymer Microdomains in Thin Films: A Review and Appraisal Wang, Hyun Suk; Kim, Ki Hyun; Bang, Joona Macromolecular Rapid Communications, Vol. 40, Issue 4 https://doi.org/10.1002/marc.201800728	journal	November 2018
Design of high-χ block copolymers for lithography Durand, William J.; Blachut, Gregory; Maher, Michael J. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 53, Issue 2 https://doi.org/10.1002/pola.27370	journal	August 2014
Well-Ordered Thin-Film Nanopore Arrays Formed Using a Block-Copolymer Template Jung, Yeon Sik; Ross, Caroline A. Small, Vol. 5, Issue 14 https://doi.org/10.1002/smll.200900053	journal	July 2009
Block copolymer thin films: pattern formation and phase behavior Green, Peter F.; Limary, Ratchana Advances in Colloid and Interface Science, Vol. 94, Issue 1-3 https://doi.org/10.1016/S0001-8686(01)00055-0	journal	November 2001
X-ray and neutron reflectivity for the investigation of polymers Russell, T. P. Materials Science Reports, Vol. 5, Issue 4 https://doi.org/10.1016/S0920-2307(05)80002-7	journal	January 1990
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
Synthesis and characterization of random copolymers of (2,2-dimethyl-1,3-dioxolan-4-yl)methyl methacrylate and 2,3-dihydroxypropyl methacrylate Kyeremateng, Samuel O.; Amado, Elkin; Kressler, Jörg European Polymer Journal, Vol. 43, Issue 8 https://doi.org/10.1016/j.eurpolymj.2007.04.048	journal	August 2007
Ultrashort-chain perfluoroalkyl substance trifluoroacetate (TFA) in beer and tea – An unintended aqueous extraction Scheurer, Marco; Nödler, Karsten Food Chemistry, Vol. 351 https://doi.org/10.1016/j.foodchem.2021.129304	journal	July 2021
Hydrolysis-Induced Self-Assembly of High-χ–Low-N Bottlebrush Copolymers Hu, Mingqiu; Li, Xindi; Rzayev, Javid Macromolecules, Vol. 54, Issue 24 https://doi.org/10.1021/acs.macromol.1c02061	journal	December 2021
Fabrication of Sub-3 nm Feature Size Based on Block Copolymer Self-Assembly for Next-Generation Nanolithography Kwak, Jongheon; Mishra, Avnish Kumar; Lee, Jaeyong Macromolecules, Vol. 50, Issue 17 https://doi.org/10.1021/acs.macromol.7b00945	journal	August 2017
Realizing 5.4 nm Full Pitch Lamellar Microdomains by a Solid-State Transformation Jeong, Gajin; Yu, Duk Man; Mapas, Jose Kenneth D. Macromolecules, Vol. 50, Issue 18 https://doi.org/10.1021/acs.macromol.7b01443	journal	September 2017
Evaluation of the Interaction Parameter for Poly(solketal methacrylate)- block -polystyrene Copolymers Yu, Duk Man; Mapas, Jose Kenneth D.; Kim, Hyeyoung Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1021/acs.macromol.7b02221	journal	January 2018
Sub-10 nm Self-Assembly of Mesogen-Containing Grafted Macromonomers and Their Bottlebrush Polymers Rokhlenko, Yekaterina; Kawamoto, Ken; Johnson, Jeremiah A. Macromolecules, Vol. 51, Issue 10 https://doi.org/10.1021/acs.macromol.8b00261	journal	May 2018
Morphological Evolution of Poly(solketal methacrylate)- block -polystyrene Copolymers in Thin Films Yu, Duk Man; Smith, Darren M.; Kim, Hyeyoung Macromolecules, Vol. 52, Issue 10 https://doi.org/10.1021/acs.macromol.9b00488	journal	May 2019
Highly Ordered Sub-10 nm Patterns Based on Multichain Columns of Side-Chain Liquid Crystalline Polymers Jiang, Xu-Qiang; Zhao, Rui-Ying; Chang, Wen-Ying Macromolecules, Vol. 52, Issue 13 https://doi.org/10.1021/acs.macromol.9b00910	journal	June 2019
Double-Patterned Sidewall Directed Self-Assembly and Pattern Transfer of Sub-10 nm PTMSS- b -PMOST Cushen, Julia; Wan, Lei; Blachut, Gregory ACS Applied Materials & Interfaces, Vol. 7, Issue 24 https://doi.org/10.1021/acsami.5b02481	journal	June 2015
High χ–Low N Block Polymers: How Far Can We Go? Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00472	journal	September 2015
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
Directed Self-Assembly and Pattern Transfer of Five Nanometer Block Copolymer Lamellae Lane, Austin P.; Yang, XiaoMin; Maher, Michael J. ACS Nano, Vol. 11, Issue 8 https://doi.org/10.1021/acsnano.7b02698	journal	July 2017
Side-Chain-Grafted Random Copolymer Brushes as Neutral Surfaces for Controlling the Orientation of Block Copolymer Microdomains in Thin Films In, Insik; La, Young-Hye; Park, Sang-Min Langmuir, Vol. 22, Issue 18 https://doi.org/10.1021/la060748g	journal	August 2006
Surface-induced orientation of symmetric, diblock copolymers: a secondary ion mass-spectrometry study Coulon, G.; Russell, T. P.; Deline, V. R. Macromolecules, Vol. 22, Issue 6 https://doi.org/10.1021/ma00196a006	journal	November 1989
Effect of Selective Perfluoroalkylation on the Segregation Strength of Polystyrene−1,2-Polybutadiene Block Copolymers Ren, Yu; Lodge, Timothy P.; Hillmyer, Marc A. Macromolecules, Vol. 35, Issue 10 https://doi.org/10.1021/ma011958x	journal	May 2002
Surface Modification with Cross-Linked Random Copolymers: Minimum Effective Thickness Ryu, Du Yeol; Wang, Jia-Yu; Lavery, Kristopher A. Macromolecules, Vol. 40, Issue 12 https://doi.org/10.1021/ma062939w	journal	May 2007
Surface Properties of Bottlebrush Polymer Thin Films Li, Xianyu; Prukop, Stacy L.; Biswal, Sibani Lisa Macromolecules, Vol. 45, Issue 17 https://doi.org/10.1021/ma301046n	journal	August 2012
Thin Film Self-Assembly of Poly(trimethylsilylstyrene- b - d , l -lactide) with Sub-10 nm Domains Cushen, Julia D.; Bates, Christopher M.; Rausch, Erica L. Macromolecules, Vol. 45, Issue 21 https://doi.org/10.1021/ma301238j	journal	October 2012
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
Sub-10 nm Scale Nanostructures in Self-Organized Linear Di- and Triblock Copolymers and Miktoarm Star Copolymers Consisting of Maltoheptaose and Polystyrene Otsuka, Issei; Zhang, Yao; Isono, Takuya Macromolecules, Vol. 48, Issue 5 https://doi.org/10.1021/ma502295y	journal	February 2015
Theory of Microphase Separation in Block Copolymers Leibler, Ludwik Macromolecules, Vol. 13, Issue 6 https://doi.org/10.1021/ma60078a047	journal	November 1980
Transition Behavior of Block Copolymer Thin Films on Preferential Surfaces Shin, Changhak; Ahn, Hyungju; Kim, Eunhye Macromolecules, Vol. 41, Issue 23 https://doi.org/10.1021/ma801778m	journal	December 2008
Unifying Weak- and Strong-Segregation Block Copolymer Theories Matsen, M. W.; Bates, F. S. Macromolecules, Vol. 29, Issue 4 https://doi.org/10.1021/ma951138i	journal	January 1996
Molecular Bottlebrushes: New Opportunities in Nanomaterials Fabrication Rzayev, Javid ACS Macro Letters, Vol. 1, Issue 9 https://doi.org/10.1021/mz300402x	journal	September 2012
Oligosaccharide/Silicon-Containing Block Copolymers with 5 nm Features for Lithographic Applications Cushen, Julia D.; Otsuka, Issei; Bates, Christopher M. ACS Nano, Vol. 6, Issue 4 https://doi.org/10.1021/nn300459r	journal	March 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
On the Self-Assembly of Brush Block Copolymers in Thin Films Hong, Sung Woo; Gu, Weiyin; Huh, June ACS Nano, Vol. 7, Issue 11 https://doi.org/10.1021/nn402639g	journal	October 2013
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries Stoykovich, Mark P.; Kang, Huiman; Daoulas, Kostas Ch. ACS Nano, Vol. 1, Issue 3 https://doi.org/10.1021/nn700164p	journal	October 2007
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
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 copolymers for 7 nanometre FinFET technology and beyond Liu, Chi-Chun; Franke, Elliott; Mignot, Yann Nature Electronics, Vol. 1, Issue 10 https://doi.org/10.1038/s41928-018-0147-4	journal	October 2018
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
Fast self-assembly of polystyrene- b -poly(fluoro methacrylate) into sub-5 nm microdomains for nanopatterning applications Li, Xuemiao; Li, Jie; Wang, Chenxu Journal of Materials Chemistry C, Vol. 7, Issue 9 https://doi.org/10.1039/C8TC06480F	journal	January 2019
Polymers with advanced architectures as emulsifiers for multi-functional emulsions Hu, Mingqiu; Russell, Thomas P. Materials Chemistry Frontiers, Vol. 5, Issue 3 https://doi.org/10.1039/D0QM00730G	journal	January 2021
Block Copolymers—Designer Soft Materials Bates, Frank S.; Fredrickson, Glenn H. Physics Today, Vol. 52, Issue 2 https://doi.org/10.1063/1.882522	journal	February 1999
Dynamics of phase separation in block copolymer melts Liu, Fong; Goldenfeld, Nigel Physical Review A, Vol. 39, Issue 9 https://doi.org/10.1103/PhysRevA.39.4805	journal	May 1989
BornAgain : software for simulating and fitting grazing-incidence small-angle scattering Pospelov, Gennady; Van Herck, Walter; Burle, Jan Journal of Applied Crystallography, Vol. 53, Issue 1 https://doi.org/10.1107/S1600576719016789	journal	February 2020
The node is nonsense Moore, Samuel K. IEEE Spectrum, Vol. 57, Issue 8 https://doi.org/10.1109/MSPEC.2020.9150552	journal	August 2020
Orientation control of high-χ triblock copolymer for sub-10 nm patterning using fluorine-containing polymeric additives Li, Jiajing; Zhou, Chun; Chen, Xuanxuan Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 18, Issue 03 https://doi.org/10.1117/1.JMM.18.3.035501	journal	July 2019
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
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
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 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
Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes Hawker, Craig J.; Russell, Thomas P. MRS Bulletin, Vol. 30, Issue 12, p. 952-966 https://doi.org/10.1557/mrs2005.249	journal	December 2005
Interactive, Web-Based Calculator of Neutron and X-ray Reflectivity Maranville, Brian B. Journal of Research of the National Institute of Standards and Technology, Vol. 122 https://doi.org/10.6028/jres.122.034	journal	January 2017

Similar Records

Using Grazing-Incidence Small-Angle Neutron Scattering to Study the Orientation of Block Copolymer Morphologies in Thin Films

Journal Article · Tue Mar 14 20:00:00 EDT 2023 · Macromolecules · OSTI ID:1965239

Bottlebrush Block Copolymer Thin Films

Journal Article · Mon Oct 13 20:00:00 EDT 2025 · Macromolecules · OSTI ID:3000968

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copolymers
hydrolysis
layers
morphology
thin films

Hydrolysis-Induced Morphology Evolution of Linear and Bottlebrush Block Copolymers in Thin Films with Acid Vapor or Photoacid Generators

Citation Formats

References (55)

Similar Records

Related Subjects