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Title: 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:
 [1];  [2];  [3];  [1];  [2];  [4];  [3];  [3];  [3];  [1];  [2]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Electrical and Computer Engineering
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  3. Univ. of Wisconsin, Madison, WI (United States). Dept. of Materials Science and Engineering
  4. 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}
}

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Works referenced in this record:

Directed self-oriented self-assembly of block copolymers using chemically modified surfaces
book, January 2015


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
  • DOI: 10.1002/adma.200803302

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
  • DOI: 10.1557/mrs2005.249

Directing the self-assembly of block copolymers
journal, October 2007


Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order
journal, February 2009


Graphoepitaxy of Spherical Domain Block Copolymer Films
journal, August 2001


Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates
journal, August 2010


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
  • DOI: 10.1002/adma.200601421

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
  • DOI: 10.1038/nature01775

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
  • DOI: 10.1126/science.1111041

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
  • DOI: 10.1002/adma.200400763

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
  • DOI: 10.1021/nn700164p

Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly
journal, August 2008


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
  • DOI: 10.1021/ma902494v

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
  • DOI: 10.1002/adma.200800826

Graphoepitaxy of Self-Assembled Block Copolymers on Two-Dimensional Periodic Patterned Templates
journal, August 2008


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
  • DOI: 10.2494/photopolymer.26.831

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
  • DOI: 10.1117/1.JMM.11.3.031302

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
  • DOI: 10.1021/ma102856t

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
  • DOI: 10.1117/12.2047585

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
  • DOI: 10.1021/acsami.5b10562

How Polymer Surface Diffusion Depends on Surface Coverage
journal, February 2007

  • Zhao, Jiang; Granick, Steve
  • Macromolecules, Vol. 40, Issue 4
  • DOI: 10.1021/ma062104l

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
  • DOI: 10.1038/nmat3709

Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene
journal, July 2008


Thermal stability studies of CVD-grown graphene nanoribbons: Defect annealing and loop formation
journal, February 2009


Impermeable Atomic Membranes from Graphene Sheets
journal, August 2008

  • Bunch, J. Scott; Verbridge, Scott S.; Alden, Jonathan S.
  • Nano Letters, Vol. 8, Issue 8
  • DOI: 10.1021/nl801457b

Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
journal, May 2009


Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium
journal, April 2014


Direct Growth of Graphene Film on Germanium Substrate
journal, August 2013

  • Wang, Gang; Zhang, Miao; Zhu, Yun
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02465

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
  • DOI: 10.1021/nn101491g

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
  • DOI: 10.1002/adma.201204131

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
  • DOI: 10.1021/nl061702a

Raman spectroscopy of graphene and graphite: Disorder, electron–phonon coupling, doping and nonadiabatic effects
journal, July 2007


Block copolymers and conventional lithography
journal, September 2006


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
  • DOI: 10.1109/TMAG.2012.2227303

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
  • DOI: 10.1021/nn101561p

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
  • DOI: 10.1021/ma500561q

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
  • DOI: 10.1021/ma302464n

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
  • DOI: 10.1021/ma100150j

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
  • DOI: 10.1038/nnano.2010.132

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
  • DOI: 10.1038/ncomms9006

Electronic and Mechanical Properties of Graphene–Germanium Interfaces Grown by Chemical Vapor Deposition
journal, October 2015


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
  • DOI: 10.1002/adma.200803302

Graphoepitaxial Assembly of Symmetric Block Copolymers on Weakly Preferential Substrates
journal, August 2010


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
  • DOI: 10.1002/adma.201204131

Electronic and Mechanical Properties of Graphene–Germanium Interfaces Grown by Chemical Vapor Deposition
journal, October 2015


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
  • DOI: 10.1021/acsami.5b10562

How Polymer Surface Diffusion Depends on Surface Coverage
journal, February 2007

  • Zhao, Jiang; Granick, Steve
  • Macromolecules, Vol. 40, Issue 4
  • DOI: 10.1021/ma062104l

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
  • DOI: 10.1021/ma500561q

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
  • DOI: 10.1021/nn101491g

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
  • DOI: 10.1021/nn101561p

Polymer Self-Assembly as a Novel Extension to Optical Lithography
journal, October 2007


A decade of R2R graphene manufacturing
journal, October 2021


Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene
journal, July 2008


Macroscopic 10-Terabit-per-Square-Inch Arrays from Block Copolymers with Lateral Order
journal, February 2009


Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils
text, January 2009


Spatially Resolved Raman Spectroscopy of Single- and Few-Layer Graphene
text, January 2006


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
  • DOI: 10.1002/mats.201900009

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
  • DOI: 10.1039/c9py00335e

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
  • DOI: 10.1039/c9sm01322a

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
  • DOI: 10.3390/nano9040579

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
  • DOI: 10.3390/nano9040579