Sequential Brush Grafting for Chemically and Dimensionally Tolerant Directed Self-Assembly of Block Copolymers
Abstract
We report a method for the directed self-assembly (DSA) of block copolymers (BCPs) in which a first BCP film deploys homopolymer brushes, or “inks”, that sequentially graft onto the substrate’s surface via the interpenetration of polymer molecules during the thermal annealing of the polymer film on top of existing polymer brushes. By selecting polymer “inks” with the desired chemistry and appropriate relative molecular weights, it is possible to use brush interpenetration as a powerful technique to generate self-registered chemical contrast patterns at the same frequency as that of the domains of the BCP. The result is a process with a higher tolerance to dimensional and chemical imperfections in the guiding patterns, which we showcase by implementing DSA using homopolymer brushes for the guiding features as opposed to more robust cross-linkable mats. We find that the use of “inks” does not compromise the line width roughness, and the quality of the DSA as a lithographic mask is verified by implementing a robust “dry lift-off” pattern transfer.
- Authors:
-
[1];
[2];
[1];
[1];
[3];
[4];
[1]
- Molecular Foundry, Lawrence Berkeley National Lab, Berkeley, California 94720, United States
- Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States
- Western Digital, San Jose, California 95119, United States
- Pritzker School of Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United States, Materials Sciences Division, Argonne National Lab, Lemont, Illinois 60439, United States
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1905654
- Alternate Identifier(s):
- OSTI ID: 1909631
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Name: ACS Applied Materials and Interfaces Journal Volume: 15 Journal Issue: 1; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; directed self-assembly; block copolymer; thin films; advanced lithography; defectivity
Citation Formats
Chang, Boyce S., Loo, Whitney S., Yu, Beihang, Dhuey, Scott, Wan, Lei, Nealey, Paul F., and Ruiz, Ricardo. Sequential Brush Grafting for Chemically and Dimensionally Tolerant Directed Self-Assembly of Block Copolymers. United States: N. p., 2022.
Web. doi:10.1021/acsami.2c16508.
Chang, Boyce S., Loo, Whitney S., Yu, Beihang, Dhuey, Scott, Wan, Lei, Nealey, Paul F., & Ruiz, Ricardo. Sequential Brush Grafting for Chemically and Dimensionally Tolerant Directed Self-Assembly of Block Copolymers. United States. https://doi.org/10.1021/acsami.2c16508
Chang, Boyce S., Loo, Whitney S., Yu, Beihang, Dhuey, Scott, Wan, Lei, Nealey, Paul F., and Ruiz, Ricardo. Mon .
"Sequential Brush Grafting for Chemically and Dimensionally Tolerant Directed Self-Assembly of Block Copolymers". United States. https://doi.org/10.1021/acsami.2c16508.
@article{osti_1905654,
title = {Sequential Brush Grafting for Chemically and Dimensionally Tolerant Directed Self-Assembly of Block Copolymers},
author = {Chang, Boyce S. and Loo, Whitney S. and Yu, Beihang and Dhuey, Scott and Wan, Lei and Nealey, Paul F. and Ruiz, Ricardo},
abstractNote = {We report a method for the directed self-assembly (DSA) of block copolymers (BCPs) in which a first BCP film deploys homopolymer brushes, or “inks”, that sequentially graft onto the substrate’s surface via the interpenetration of polymer molecules during the thermal annealing of the polymer film on top of existing polymer brushes. By selecting polymer “inks” with the desired chemistry and appropriate relative molecular weights, it is possible to use brush interpenetration as a powerful technique to generate self-registered chemical contrast patterns at the same frequency as that of the domains of the BCP. The result is a process with a higher tolerance to dimensional and chemical imperfections in the guiding patterns, which we showcase by implementing DSA using homopolymer brushes for the guiding features as opposed to more robust cross-linkable mats. We find that the use of “inks” does not compromise the line width roughness, and the quality of the DSA as a lithographic mask is verified by implementing a robust “dry lift-off” pattern transfer.},
doi = {10.1021/acsami.2c16508},
journal = {ACS Applied Materials and Interfaces},
number = 1,
volume = 15,
place = {United States},
year = {Mon Dec 19 00:00:00 EST 2022},
month = {Mon Dec 19 00:00:00 EST 2022}
}
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Works referenced in this record:
Fabrication of Lithographically Defined Chemically Patterned Polymer Brushes and Mats
journal, April 2011
- Liu, Chi-Chun; Han, Eungnak; Onses, M. Serdar
- Macromolecules, Vol. 44, Issue 7
Defect source analysis of directed self-assembly process (DSA of DSA)
conference, March 2013
- Rincon Delgadillo, Paulina; Harukawa, Ryota; Suri, Mayur
- SPIE Advanced Lithography, SPIE Proceedings
Engineering the Kinetics of Directed Self-Assembly of Block Copolymers toward Fast and Defect-Free Assembly
journal, June 2018
- Ren, Jiaxing; Zhou, Chun; Chen, Xuanxuan
- ACS Applied Materials & Interfaces, Vol. 10, Issue 27
Line Roughness in Lamellae-Forming Block Copolymer Films
journal, January 2017
- Ruiz, Ricardo; Wan, Lei; Lopez, Rene
- Macromolecules, Vol. 50, Issue 3
Engineering the domain roughness of block copolymer in directed self-assembly
journal, May 2022
- Lai, Hanwen; Huang, Guangcheng; Tian, Xin
- Polymer, Vol. 249
28 nm pitch of line/space pattern transfer into silicon substrates with chemo-epitaxy Directed Self-Assembly (DSA) process flow
journal, July 2014
- Chan, Boon Teik; Tahara, Shigeru; Parnell, Doni
- Microelectronic Engineering, Vol. 123
High χ–Low N Block Polymers: How Far Can We Go?
journal, September 2015
- Sinturel, Christophe; Bates, Frank S.; Hillmyer, Marc A.
- ACS Macro Letters, Vol. 4, Issue 9
Path to Move Beyond the Resolution Limit with Directed Self-Assembly
journal, May 2019
- Wan, Lei; Ruiz, Ricardo
- ACS Applied Materials & Interfaces, Vol. 11, Issue 22
Degree of Perfection and Pattern Uniformity in the Directed Assembly of Cylinder-Forming Block Copolymer on Chemically Patterned Surfaces
journal, December 2011
- Kang, Huiman; Craig, Gordon S. W.; Han, Eungnak
- Macromolecules, Vol. 45, Issue 1
Self-Registered Self-Assembly of Block Copolymers
journal, July 2017
- Wan, Lei; Ruiz, Ricardo; Gao, He
- ACS Nano, Vol. 11, Issue 8
Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films
journal, September 2018
- Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo
- ACS Nano, Vol. 12, Issue 10
Molecular pathways for defect annihilation in directed self-assembly
journal, October 2015
- Hur, Su-Mi; Thapar, Vikram; Ramírez-Hernández, Abelardo
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 46
Three-Tone Chemical Patterns for Block Copolymer Directed Self-Assembly
journal, January 2016
- Williamson, Lance D.; Seidel, Robert N.; Chen, Xuanxuan
- ACS Applied Materials & Interfaces, Vol. 8, Issue 4
Controlling Polymer-Surface Interactions with Random Copolymer Brushes
journal, March 1997
- Mansky, P.; Liu, Y.; Huang, E.
- Science, Vol. 275, Issue 5305, p. 1458-1460
Need for LWR metrology standardization: the imec roughness protocol
journal, September 2018
- Lorusso, Gian Francesco; Sutani, Takumichi; Rutigliani, Vito
- Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 17, Issue 04
Photopatternable Imaging Layers for Controlling Block Copolymer Microdomain Orientation
journal, December 2007
- Han, E.; In, I.; Park, S. -M.
- Advanced Materials, Vol. 19, Issue 24
Interpolation in the Directed Assembly of Block Copolymers on Nanopatterned Substrates: Simulation and Experiments
journal, April 2010
- Detcheverry, François A.; Liu, Guoliang; Nealey, Paul F.
- Macromolecules, Vol. 43, Issue 7
Fabrication of nanostructures with long-range order using block copolymer lithography
journal, November 2002
- Cheng, J. Y.; Ross, C. A.; Thomas, E. L.
- Applied Physics Letters, Vol. 81, Issue 19, p. 3657-3659
Understanding Kinetics of Defect Annihilation in Chemoepitaxy-Directed Self-Assembly
journal, May 2021
- Li, Jiajing; Rincon-Delgadillo, Paulina A.; Suh, Hyo Seon
- ACS Applied Materials & Interfaces, Vol. 13, Issue 21
Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates
journal, July 2003
- Ouk Kim, Sang; Solak, Harun H.; Stoykovich, Mark P.
- Nature, Vol. 424, Issue 6947, p. 411-414
Chemical Patterns for Directed Self-Assembly of Lamellae-Forming Block Copolymers with Density Multiplication of Features
journal, February 2013
- Liu, Chi-Chun; Ramírez-Hernández, Abelardo; Han, Eungnak
- Macromolecules, Vol. 46, Issue 4
Monte Carlo Simulations of a Coarse Grain Model for Block Copolymers and Nanocomposites
journal, July 2008
- Detcheverry, François A.; Kang, Huiman; Daoulas, Kostas Ch.
- Macromolecules, Vol. 41, Issue 13
Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly
journal, August 2008
- Ruiz, R.; Kang, H.; Detcheverry, F. A.
- Science, Vol. 321, Issue 5891
The Limits of Lamellae-Forming PS- b -PMMA Block Copolymers for Lithography
journal, June 2015
- Wan, Lei; Ruiz, Ricardo; Gao, He
- ACS Nano, Vol. 9, Issue 7
Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains
journal, December 2008
- Han, Eungnak; Stuen, Karl O.; La, Young-Hye
- Macromolecules, Vol. 41, Issue 23
Remediation of Line Edge Roughness in Chemical Nanopatterns by the Directed Assembly of Overlying Block Copolymer Films
journal, March 2010
- Stoykovich, Mark P.; Daoulas, Kostas Ch.; Müller, Marcus
- Macromolecules, Vol. 43, Issue 5
Molecular Transfer Printing Using Block Copolymers
journal, December 2009
- Ji, Shengxiang; Liu, Chi-Chun; Liu, Guoliang
- ACS Nano, Vol. 4, Issue 2
Planarizing material for reverse-tone step and flash imprint lithography
journal, July 2014
- Ogawa, Tsuyoshi; Jacobsson, B. Michael; Deschner, Ryan
- Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 13, Issue 3
Free energy of defects in chemoepitaxial block copolymer directed self-assembly: effect of pattern density and defect position
conference, April 2017
- Nation, Benjamin D.; Breaux, Caleb L.; Ludovice, Peter J.
- SPIE Proceedings
Development of silicon glass for etch reverse layer (SiGERL) materials and BARCs for double patterning process
conference, December 2009
- Sakaida, Yasushi; Yaguchi, Hiroaki; Sakamoto, Rikimaru
- SPIE Proceedings
Process sensitivities in exemplary chemo-epitaxy directed self-assembly integration
conference, March 2013
- Rincon Delgadillo, Paulina A.; Gronheid, Roel; Lin, Guanyang
- Alternative Lithographic Technologies V
Evidence of Mechanochemical Control in “Grafting to” Reactions of Hydroxy-Terminated Statistical Copolymers
journal, December 2020
- Laus, Michele; Chiarcos, Riccardo; Gianotti, Valentina
- Macromolecules, Vol. 54, Issue 1
Tuning the strength of chemical patterns for directed self-assembly of block copolymers
conference, March 2014
- Williamson, Lance; Lin, Guanyang; Cao, Yi
- SPIE Advanced Lithography, SPIE Proceedings
Defect reduction and defect stability in IMEC's 14nm half-pitch chemo-epitaxy DSA flow
conference, March 2014
- Gronheid, Roel; Rincon Delgadillo, Paulina; Pathangi, Hari
- SPIE Advanced Lithography, SPIE Proceedings
Quantitative Three-Dimensional Characterization of Block Copolymer Directed Self-Assembly on Combined Chemical and Topographical Prepatterned Templates
journal, January 2017
- Segal-Peretz, Tamar; Ren, Jiaxing; Xiong, Shisheng
- ACS Nano, Vol. 11, Issue 2
Modification of a polystyrene brush layer by insertion of poly(methyl methacrylate) molecules
journal, January 2009
- Liu, Guoliang; Ji, Shengxiang; Stuen, Karl O.
- Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 27, Issue 6
Interfacial Design for Block Copolymer Thin Films
journal, January 2014
- Maher, Michael J.; Bates, Christopher M.; Blachut, Gregory
- Chemistry of Materials, Vol. 26, Issue 3
Development of a robust reverse tone pattern transfer process
conference, March 2017
- Khusnatdinov, Niyaz; Doyle, Gary; Resnick, Douglas J.
- SPIE Proceedings
Three-dimensional line edge roughness in pre- and post-dry etch line and space patterns of block copolymer lithography
journal, January 2020
- Pinge, Shubham; Qiu, Yufeng; Monreal, Victor
- Physical Chemistry Chemical Physics, Vol. 22, Issue 2