Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns
Abstract
Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyreneblock-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. Lastly, the rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.
- Authors:
-
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Electrical and Computer Engineering
- Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
- Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering
- Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; IBM Albany NanoTech, Albany, NY (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOD; US Air Force Office of Scientific Research (AFOSR)
- OSTI Identifier:
- 1436420
- Grant/Contract Number:
- SC0006414
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Scientific Reports
- Additional Journal Information:
- Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2045-2322
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Chang, Tzu-Hsuan, Xiong, Shisheng, Jacobberger, Robert M., Mikael, Solomon, Suh, Hyo Seon, Liu, Chi-Chun, Geng, Dalong, Wang, Xudong, Arnold, Michael S., Ma, Zhenqiang, and Nealey, Paul F. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns. United States: N. p., 2016.
Web. doi:10.1038/srep31407.
Chang, Tzu-Hsuan, Xiong, Shisheng, Jacobberger, Robert M., Mikael, Solomon, Suh, Hyo Seon, Liu, Chi-Chun, Geng, Dalong, Wang, Xudong, Arnold, Michael S., Ma, Zhenqiang, & Nealey, Paul F. Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns. United States. https://doi.org/10.1038/srep31407
Chang, Tzu-Hsuan, Xiong, Shisheng, Jacobberger, Robert M., Mikael, Solomon, Suh, Hyo Seon, Liu, Chi-Chun, Geng, Dalong, Wang, Xudong, Arnold, Michael S., Ma, Zhenqiang, and Nealey, Paul F. Tue .
"Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns". United States. https://doi.org/10.1038/srep31407. https://www.osti.gov/servlets/purl/1436420.
@article{osti_1436420,
title = {Directed self-assembly of block copolymer films on atomically-thin graphene chemical patterns},
author = {Chang, Tzu-Hsuan and Xiong, Shisheng and Jacobberger, Robert M. and Mikael, Solomon and Suh, Hyo Seon and Liu, Chi-Chun and Geng, Dalong and Wang, Xudong and Arnold, Michael S. and Ma, Zhenqiang and Nealey, Paul F.},
abstractNote = {Directed self-assembly of block copolymers is a scalable method to fabricate well-ordered patterns over the wafer scale with feature sizes below the resolution of conventional lithography. Typically, lithographically-defined prepatterns with varying chemical contrast are used to rationally guide the assembly of block copolymers. The directed self-assembly to obtain accurate registration and alignment is largely influenced by the assembly kinetics. Furthermore, a considerably broad processing window is favored for industrial manufacturing. Using an atomically-thin layer of graphene on germanium, after two simple processing steps, we create a novel chemical pattern to direct the assembly of polystyreneblock-poly(methyl methacrylate). Faster assembly kinetics are observed on graphene/germanium chemical patterns than on conventional chemical patterns based on polymer mats and brushes. This new chemical pattern allows for assembly on a wide range of guiding periods and along designed 90° bending structures. We also achieve density multiplication by a factor of 10, greatly enhancing the pattern resolution. Lastly, the rapid assembly kinetics, minimal topography, and broad processing window demonstrate the advantages of inorganic chemical patterns composed of hard surfaces.},
doi = {10.1038/srep31407},
journal = {Scientific Reports},
number = 1,
volume = 6,
place = {United States},
year = {Tue Aug 16 00:00:00 EDT 2016},
month = {Tue Aug 16 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Directed self-oriented self-assembly of block copolymers using chemically modified surfaces
book, January 2015
- Seidel, R.; Williamson, L.; Segal-Peretz, T.
- Directed Self-assembly of Block Co-polymers for Nano-manufacturing
Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns
journal, July 2009
- Bang, Joona; Jeong, Unyong; Ryu, Du Yeol
- Advanced Materials, Vol. 21, Issue 47, p. 4769-4792
Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes
journal, December 2005
- Hawker, Craig J.; Russell, Thomas P.
- MRS Bulletin, Vol. 30, Issue 12, p. 952-966
Directing the self-assembly of block copolymers
journal, October 2007
- Darling, S. B.
- Progress in Polymer Science, Vol. 32, Issue 10
Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order
journal, February 2009
- Park, Soojin; Lee, Dong Hyun; Xu, Ji
- Science, Vol. 323, Issue 5917, p. 1030-1033
Graphoepitaxy of Spherical Domain Block Copolymer Films
journal, August 2001
- Segalman, R. A.; Yokoyama, H.; Kramer, E. J.
- Advanced Materials, Vol. 13, Issue 15, p. 1152-1155
Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates
journal, August 2010
- Han, Eungnak; Kang, Huiman; Liu, Chi-Chun
- Advanced Materials, Vol. 22, Issue 38
Directed Assembly of Lamellae- Forming Block Copolymers by Using Chemically and Topographically Patterned Substrates
journal, February 2007
- Park, S. -M.; Stoykovich, M. P.; Ruiz, R.
- Advanced Materials, Vol. 19, Issue 4
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
Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures
journal, June 2005
- Stoykovich, Mark P.; Müller, Marcus; Kim, Sang Ouk
- Science, Vol. 308, Issue 5727, p. 1442-1446
Precise Control over Molecular Dimensions of Block-Copolymer Domains Using the Interfacial Energy of Chemically Nanopatterned Substrates
journal, August 2004
- Edwards, E. W.; Montague, M. F.; Solak, H. H.
- Advanced Materials, Vol. 16, Issue 15
Directed Self-Assembly of Block Copolymers for Nanolithography: Fabrication of Isolated Features and Essential Integrated Circuit Geometries
journal, October 2007
- Stoykovich, Mark P.; Kang, Huiman; Daoulas, Kostas Ch.
- ACS Nano, Vol. 1, Issue 3
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
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
Dense Self-Assembly on Sparse Chemical Patterns: Rectifying and Multiplying Lithographic Patterns Using Block Copolymers
journal, August 2008
- Cheng, Joy Y.; Rettner, Charles T.; Sanders, Daniel P.
- Advanced Materials, Vol. 20, Issue 16
Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates
journal, August 2008
- Bita, I.; Yang, J. K. W.; Jung, Y. S.
- Science, Vol. 321, Issue 5891
Scale-up of a Chemo-Epitaxy Flow for Feature Multiplication Using Directed Self- Assembly of Block-Copolymers
journal, January 2013
- Rincon-Delgadillo, Paulina; Craig, Gordon; Gronheid, Roel
- Journal of Photopolymer Science and Technology, Vol. 26, Issue 6
Implementation of a chemo-epitaxy flow for directed self-assembly on 300-mm wafer processing equipment
journal, July 2012
- Delgadillo, Paulina A. Rincon
- Journal of Micro/Nanolithography, MEMS, and MOEMS, Vol. 11, Issue 3
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
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
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
How Polymer Surface Diffusion Depends on Surface Coverage
journal, February 2007
- Zhao, Jiang; Granick, Steve
- Macromolecules, Vol. 40, Issue 4
Wetting and Interfacial Properties of Water Nanodroplets in Contact with Graphene and Monolayer Boron–Nitride Sheets
journal, February 2012
- Li, Hui; Zeng, Xiao Cheng
- ACS Nano, Vol. 6, Issue 3
Effect of airborne contaminants on the wettability of supported graphene and graphite
journal, July 2013
- Li, Zhiting; Wang, Yongjin; Kozbial, Andrew
- Nature Materials, Vol. 12, Issue 10
Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene
journal, July 2008
- Lee, C.; Wei, X.; Kysar, J. W.
- Science, Vol. 321, Issue 5887, p. 385-388
Thermal stability studies of CVD-grown graphene nanoribbons: Defect annealing and loop formation
journal, February 2009
- Campos-Delgado, J.; Kim, Y. A.; Hayashi, T.
- Chemical Physics Letters, Vol. 469, Issue 1-3
Impermeable Atomic Membranes from Graphene Sheets
journal, August 2008
- Bunch, J. Scott; Verbridge, Scott S.; Alden, Jonathan S.
- Nano Letters, Vol. 8, Issue 8
Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
journal, May 2009
- Li, X.; Cai, W.; An, J.
- Science, Vol. 324, Issue 5932, p. 1312-1314
Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium
journal, April 2014
- Lee, J.-H.; Lee, E. K.; Joo, W.-J.
- Science, Vol. 344, Issue 6181, p. 286-289
Direct Growth of Graphene Film on Germanium Substrate
journal, August 2013
- Wang, Gang; Zhang, Miao; Zhu, Yun
- Scientific Reports, Vol. 3, Issue 1
Surface Energy Modification by Spin-Cast, Large-Area Graphene Film for Block Copolymer Lithography
journal, August 2010
- Kim, Bong Hoon; Kim, Ju Young; Jeong, Seong-Jun
- ACS Nano, Vol. 4, Issue 9
Flexible and Transferrable Self-Assembled Nanopatterning on Chemically Modified Graphene
journal, December 2012
- Kim, Ju Young; Kim, Bong Hoon; Hwang, Jin Ok
- Advanced Materials, Vol. 25, Issue 9
Spatially Resolved Raman Spectroscopy of Single- and Few-Layer Graphene
journal, February 2007
- Graf, D.; Molitor, F.; Ensslin, K.
- Nano Letters, Vol. 7, Issue 2, p. 238-242
Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007
- Ferrari, Andrea C.
- Solid State Communications, Vol. 143, Issue 1-2, p. 47-57
Block copolymers and conventional lithography
journal, September 2006
- Stoykovich, Mark P.; Nealey, Paul F.
- Materials Today, Vol. 9, Issue 9, p. 20-29
Bit Patterned Media at 1 Tdot/in$^{2}$ and Beyond
journal, February 2013
- Albrecht, Thomas R.; Bedau, Daniel; Dobisz, Elizabeth
- IEEE Transactions on Magnetics, Vol. 49, Issue 2
Rectangular Patterns Using Block Copolymer Directed Assembly for High Bit Aspect Ratio Patterned Media
journal, December 2010
- Ruiz, Ricardo; Dobisz, Elizabeth; Albrecht, Thomas R.
- ACS Nano, Vol. 5, Issue 1
Enhancing Ordering Dynamics in Solvent-Annealed Block Copolymer Films by Lithographic Hard Mask Supports
journal, April 2014
- Stenbock-Fermor, Anja; Knoll, Armin W.; Böker, Alexander
- Macromolecules, Vol. 47, Issue 9
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
Thickness Dependence of Neutral Parameter Windows for Perpendicularly Oriented Block Copolymer Thin Films
journal, May 2010
- Suh, Hyo Seon; Kang, Huiman; Nealey, Paul F.
- Macromolecules, Vol. 43, Issue 10
Roll-to-roll production of 30-inch graphene films for transparent electrodes
journal, June 2010
- Bae, Sukang; Kim, Hyeongkeun; Lee, Youngbin
- Nature Nanotechnology, Vol. 5, Issue 8, p. 574-578
Direct oriented growth of armchair graphene nanoribbons on germanium
journal, August 2015
- Jacobberger, Robert M.; Kiraly, Brian; Fortin-Deschenes, Matthieu
- Nature Communications, Vol. 6, Article No. 8006
Electronic and Mechanical Properties of Graphene–Germanium Interfaces Grown by Chemical Vapor Deposition
journal, October 2015
- Kiraly, Brian; Jacobberger, Robert M.; Mannix, Andrew J.
- Nano Letters, Vol. 15, Issue 11
Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns
journal, July 2009
- Bang, Joona; Jeong, Unyong; Ryu, Du Yeol
- Advanced Materials, Vol. 21, Issue 47, p. 4769-4792
Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates
journal, August 2010
- Han, Eungnak; Kang, Huiman; Liu, Chi-Chun
- Advanced Materials, Vol. 22, Issue 38
Flexible and Transferrable Self-Assembled Nanopatterning on Chemically Modified Graphene
journal, December 2012
- Kim, Ju Young; Kim, Bong Hoon; Hwang, Jin Ok
- Advanced Materials, Vol. 25, Issue 9
Electronic and Mechanical Properties of Graphene–Germanium Interfaces Grown by Chemical Vapor Deposition
journal, October 2015
- Kiraly, Brian; Jacobberger, Robert M.; Mannix, Andrew J.
- Nano Letters, Vol. 15, Issue 11
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
How Polymer Surface Diffusion Depends on Surface Coverage
journal, February 2007
- Zhao, Jiang; Granick, Steve
- Macromolecules, Vol. 40, Issue 4
Enhancing Ordering Dynamics in Solvent-Annealed Block Copolymer Films by Lithographic Hard Mask Supports
journal, April 2014
- Stenbock-Fermor, Anja; Knoll, Armin W.; Böker, Alexander
- Macromolecules, Vol. 47, Issue 9
Surface Energy Modification by Spin-Cast, Large-Area Graphene Film for Block Copolymer Lithography
journal, August 2010
- Kim, Bong Hoon; Kim, Ju Young; Jeong, Seong-Jun
- ACS Nano, Vol. 4, Issue 9
Rectangular Patterns Using Block Copolymer Directed Assembly for High Bit Aspect Ratio Patterned Media
journal, December 2010
- Ruiz, Ricardo; Dobisz, Elizabeth; Albrecht, Thomas R.
- ACS Nano, Vol. 5, Issue 1
Wetting and Interfacial Properties of Water Nanodroplets in Contact with Graphene and Monolayer Boron–Nitride Sheets
journal, February 2012
- Li, Hui; Zeng, Xiao Cheng
- ACS Nano, Vol. 6, Issue 3
Polymer Self-Assembly as a Novel Extension to Optical Lithography
journal, October 2007
- Black, Charles T.
- ACS Nano, Vol. 1, Issue 3
A decade of R2R graphene manufacturing
journal, October 2021
- Bubnova, Olga
- Nature Nanotechnology, Vol. 16, Issue 10
Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene
journal, July 2008
- Lee, C.; Wei, X.; Kysar, J. W.
- Science, Vol. 321, Issue 5887, p. 385-388
Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order
journal, February 2009
- Park, Soojin; Lee, Dong Hyun; Xu, Ji
- Science, Vol. 323, Issue 5917, p. 1030-1033
Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
text, January 2009
- Li, Xuesong; Cai, Weiwei; An, Jinho
- arXiv
Spatially Resolved Raman Spectroscopy of Single- and Few-Layer Graphene
text, January 2006
- Graf, D.; Molitor, F.; Ensslin, K.
- arXiv
Works referencing / citing this record:
Graphoepitaxial Assembly of Block Copolymer for Bending Stripe Patterns
journal, April 2019
- Huh, June; Kim, Mi‐Jeong; Park, Jong‐Wan
- Macromolecular Theory and Simulations, Vol. 28, Issue 4
Hierarchical patterns with sub-20 nm pattern fidelity via block copolymer self-assembly and soft nanotransfer printing
journal, January 2019
- Tran, Helen; Bergman, Harrison M.; Parenti, Kaia R.
- Polymer Chemistry, Vol. 10, Issue 23
Automated solvent vapor annealing with nanometer scale control of film swelling for block copolymer thin films
journal, January 2019
- Hulkkonen, Hanna; Salminen, Turkka; Niemi, Tapio
- Soft Matter, Vol. 15, Issue 39
Large-Area Biomolecule Nanopatterns on Diblock Copolymer Surfaces for Cell Adhesion Studies
journal, April 2019
- Hortigüela, Verónica; Larrañaga, Enara; Lagunas, Anna
- Nanomaterials, Vol. 9, Issue 4
Large-Area Biomolecule Nanopatterns on Diblock Copolymer Surfaces for Cell Adhesion Studies
journal, April 2019
- Hortigüela, Verónica; Larrañaga, Enara; Lagunas, Anna
- Nanomaterials, Vol. 9, Issue 4