DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat

Abstract

Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocks of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. As a result, the ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications.

Authors:
 [1];  [2];  [2];  [1]; ORCiD logo [3];  [3];  [2];  [1]
  1. Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Materials Sciences and Engineering Division; National Science Foundation (NSF); U.S. Army Research Laboratory - U.S. Army Research Office (ARO)
OSTI Identifier:
1373307
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Nanotechnology
Additional Journal Information:
Journal Volume: 12; Journal Issue: 6; Journal ID: ISSN 1748-3387
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Suh, Hyo Seon, Kim, Do Han, Moni, Priya, Xiong, Shisheng, Ocola, Leonidas E., Zaluzec, Nestor J., Gleason, Karen K., and Nealey, Paul F. Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat. United States: N. p., 2017. Web. doi:10.1038/nnano.2017.34.
Suh, Hyo Seon, Kim, Do Han, Moni, Priya, Xiong, Shisheng, Ocola, Leonidas E., Zaluzec, Nestor J., Gleason, Karen K., & Nealey, Paul F. Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat. United States. https://doi.org/10.1038/nnano.2017.34
Suh, Hyo Seon, Kim, Do Han, Moni, Priya, Xiong, Shisheng, Ocola, Leonidas E., Zaluzec, Nestor J., Gleason, Karen K., and Nealey, Paul F. Mon . "Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat". United States. https://doi.org/10.1038/nnano.2017.34. https://www.osti.gov/servlets/purl/1373307.
@article{osti_1373307,
title = {Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat},
author = {Suh, Hyo Seon and Kim, Do Han and Moni, Priya and Xiong, Shisheng and Ocola, Leonidas E. and Zaluzec, Nestor J. and Gleason, Karen K. and Nealey, Paul F.},
abstractNote = {Directed self-assembly (DSA) of the domain structure in block copolymer (BCP) thin films is a promising approach for sub-10-nm surface patterning. DSA requires the control of interfacial properties on both interfaces of a BCP film to induce the formation of domains that traverse the entire film with a perpendicular orientation. Here we show a methodology to control the interfacial properties of BCP films that uses a polymer topcoat deposited by initiated chemical vapour deposition (iCVD). The iCVD topcoat forms a crosslinked network that grafts to and immobilizes BCP chains to create an interface that is equally attractive to both blocks of the underlying copolymer. The topcoat, in conjunction with a chemically patterned substrate, directs the assembly of the grating structures in BCP films with a half-pitch dimension of 9.3 nm. As the iCVD topcoat can be as thin as 7 nm, it is amenable to pattern transfer without removal. As a result, the ease of vapour-phase deposition, applicability to high-resolution BCP systems and integration with pattern-transfer schemes are attractive properties of iCVD topcoats for industrial applications.},
doi = {10.1038/nnano.2017.34},
journal = {Nature Nanotechnology},
number = 6,
volume = 12,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2017},
month = {Mon Mar 27 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 131 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


Topcoat Approaches for Directed Self-Assembly of Strongly Segregating Block Copolymer Thin Films
journal, January 2013

  • Yoshida, Hiroshi; Suh, Hyo Seon; Ramirez-Herunandez, Abelardo
  • Journal of Photopolymer Science and Technology, Vol. 26, Issue 1
  • DOI: 10.2494/photopolymer.26.55

High χ–Low N Block Polymers: How Far Can We Go?
journal, September 2015


Initiated and Oxidative Chemical Vapor Deposition of Polymeric Thin Films: iCVD and oCVD
journal, April 2008

  • Tenhaeff, Wyatt E.; Gleason, Karen K.
  • Advanced Functional Materials, Vol. 18, Issue 7
  • DOI: 10.1002/adfm.200701479

Directed Self-Assembly of Triblock Copolymer on Chemical Patterns for Sub-10-nm Nanofabrication via Solvent Annealing
journal, July 2016


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

Molecular Transfer Printing of Block Copolymer Patterns over Large Areas with Conformal Layers
journal, May 2015

  • Inoue, Takejiro; Janes, Dustin W.; Ren, Jiaxing
  • Advanced Materials Interfaces, Vol. 2, Issue 10
  • DOI: 10.1002/admi.201500133

Towards electrical testable SOI devices using Directed Self-Assembly for fin formation
conference, March 2014

  • Liu, Chi-Chun; Estrada-Raygoza, Cristina; He, Hong
  • SPIE Advanced Lithography, SPIE Proceedings
  • DOI: 10.1117/12.2046462

A Route Towards Sustainability Through Engineered Polymeric Interfaces
journal, May 2014

  • Reeja-Jayan, B.; Kovacik, Peter; Yang, Rong
  • Advanced Materials Interfaces, Vol. 1, Issue 4
  • DOI: 10.1002/admi.201400117

Decoupling Bulk Thermodynamics and Wetting Characteristics of Block Copolymer Thin Films
journal, November 2011

  • Kim, Sangwon; Nealey, Paul F.; Bates, Frank S.
  • ACS Macro Letters, Vol. 1, Issue 1
  • DOI: 10.1021/mz2000169

20nm Pitch Directed Block Copolymer Assembly Using Solvent Annealing for Bit Patterned Media
journal, January 2010

  • Bosworth, Joan K.; Dobisz, Elizabeth; Ruiz, Ricardo
  • Journal of Photopolymer Science and Technology, Vol. 23, Issue 2
  • DOI: 10.2494/photopolymer.23.145

Initiated Chemical Vapor Deposition (iCVD) of Poly(alkyl acrylates):  An Experimental Study
journal, May 2006

  • Lau, Kenneth K. S.; Gleason, Karen K.
  • Macromolecules, Vol. 39, Issue 10
  • DOI: 10.1021/ma0601619

Solvent Vapor Annealing of Block Polymer Thin Films
journal, June 2013

  • Sinturel, Christophe; Vayer, Marylène; Morris, Michael
  • Macromolecules, Vol. 46, Issue 14
  • DOI: 10.1021/ma400735a

Double-Patterned Sidewall Directed Self-Assembly and Pattern Transfer of Sub-10 nm PTMSS- b -PMOST
journal, June 2015

  • Cushen, Julia; Wan, Lei; Blachut, Gregory
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 24
  • DOI: 10.1021/acsami.5b02481

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


Organic Vapor Passivation of Silicon at Room Temperature
journal, January 2013

  • Yang, Rong; Buonassisi, Tonio; Gleason, Karen K.
  • Advanced Materials, Vol. 25, Issue 14
  • DOI: 10.1002/adma.201204382

Highly Oriented and Ordered Arrays from Block Copolymers via Solvent Evaporation
journal, February 2004

  • Kim, S. H.; Misner, M. J.; Xu, T.
  • Advanced Materials, Vol. 16, Issue 3, p. 226-231
  • DOI: 10.1002/adma.200304906

Polarity-Switching Top Coats Enable Orientation of Sub-10-nm Block Copolymer Domains
journal, November 2012


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

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

The Limits of Lamellae-Forming PS- b -PMMA Block Copolymers for Lithography
journal, June 2015


Generalization of the Use of Random Copolymers To Control the Wetting Behavior of Block Copolymer Films
journal, December 2008

  • Ji, Shengxiang; Liu, Chi-Chun; Son, Jeong Gon
  • Macromolecules, Vol. 41, Issue 23
  • DOI: 10.1021/ma801861h

Plasma etch transfer of self-assembled polymer patterns
journal, July 2012


Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate)
journal, May 1990

  • Russell, Thomas P.; Hjelm, Rex P.; Seeger, Phil A.
  • Macromolecules, Vol. 23, Issue 3
  • DOI: 10.1021/ma00205a033

Free-Radical Approach to 4-Substituted Dipicolinates
journal, April 2005

  • Shelkov, Rimma; Melman, Artem
  • European Journal of Organic Chemistry, Vol. 2005, Issue 7
  • DOI: 10.1002/ejoc.200400637

Transition between kinetic and mass transfer regimes in the initiated chemical vapor deposition from ethylene glycol diacrylate
journal, September 2009

  • Ozaydin-Ince, Gozde; Gleason, Karen K.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 27, Issue 5
  • DOI: 10.1116/1.3168553

Control of Directed Self-Assembly in Block Polymers by Polymeric Topcoats
journal, May 2014

  • Ramírez-Hernández, Abelardo; Suh, Hyo Seon; Nealey, Paul F.
  • Macromolecules, Vol. 47, Issue 10
  • DOI: 10.1021/ma500411q

Large-scale initiated chemical vapor deposition of poly(glycidyl methacrylate) thin films
journal, December 2006


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

Directed Self-Assembly of Silicon-Containing Block Copolymer Thin Films
journal, January 2015

  • Maher, Michael J.; Rettner, Charles T.; Bates, Christopher M.
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 5
  • DOI: 10.1021/am508197k

SAXS Analysis of the Order−Disorder Transition and the Interaction Parameter of Polystyrene- block -poly(methyl methacrylate)
journal, December 2008

  • Zhao, Yue; Sivaniah, Easan; Hashimoto, Takeji
  • Macromolecules, Vol. 41, Issue 24
  • DOI: 10.1021/ma8013004

Two-Dimensional Pattern Formation Using Graphoepitaxy of PS- b -PMMA Block Copolymers for Advanced FinFET Device and Circuit Fabrication
journal, April 2014

  • Tsai, Hsinyu; Pitera, Jed W.; Miyazoe, Hiroyuki
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn501300b

Controllable Cross-Linking of Vapor-Deposited Polymer Thin Films and Impact on Material Properties
journal, February 2013

  • Petruczok, Christy D.; Yang, Rong; Gleason, Karen K.
  • Macromolecules, Vol. 46, Issue 5
  • DOI: 10.1021/ma302566r

Nucleophilic character of alkyl radicals—VI
journal, January 1971


X-ray and neutron reflectivity for the investigation of polymers
journal, January 1990


25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication
journal, September 2013

  • Coclite, Anna Maria; Howden, Rachel M.; Borrelli, David C.
  • Advanced Materials, Vol. 25, Issue 38
  • DOI: 10.1002/adma.201301878

Experimental and Modeling Study of Domain Orientation in Confined Block Copolymer Thin Films
journal, December 2015


Current Trends and Challenges in Biointerfaces Science and Engineering
journal, July 2015


Nanoscopic Patterned Materials with Tunable Dimensions via Atomic Layer Deposition on Block Copolymers
journal, September 2010

  • Peng, Qing; Tseng, Yu-Chih; Darling, Seth B.
  • Advanced Materials, Vol. 22, Issue 45, p. 5129-5133
  • DOI: 10.1002/adma.201002465

Works referencing / citing this record:

Thermodynamic and Kinetic Tuning of Block Copolymer Based on Random Copolymerization for High-Quality Sub-6 nm Pattern Formation
journal, May 2018

  • Hur, Yoon Hyung; Song, Seung Won; Kim, Jong Min
  • Advanced Functional Materials, Vol. 28, Issue 28
  • DOI: 10.1002/adfm.201800765

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy
journal, March 2019

  • Park, Kangho; Jung, Woo‐Bin; Kwon, Kiok
  • Advanced Functional Materials, Vol. 29, Issue 26
  • DOI: 10.1002/adfm.201901876

Smart Nanostructured Materials based on Self‐Assembly of Block Copolymers
journal, June 2019

  • Kim, Jang Hwan; Jin, Hyeong Min; Yang, Geon Gug
  • Advanced Functional Materials, Vol. 30, Issue 2
  • DOI: 10.1002/adfm.201902049

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties
journal, May 2018


Hydrogen Bond Induces Hierarchical Self-Assembly in Liquid-Crystalline Block Copolymers
journal, February 2018

  • Huang, Shuai; Pang, Linlin; Chen, Yuxuan
  • Macromolecular Rapid Communications, Vol. 39, Issue 6
  • DOI: 10.1002/marc.201700783

Thermal Approaches to Perpendicular Block Copolymer Microdomains in Thin Films: A Review and Appraisal
journal, November 2018

  • Wang, Hyun Suk; Kim, Ki Hyun; Bang, Joona
  • Macromolecular Rapid Communications, Vol. 40, Issue 4
  • DOI: 10.1002/marc.201800728

High‐Fidelity, Sub‐5 nm Patterns from High‐χ Block Copolymer Films with Vapor‐Deposited Ultrathin, Cross‐Linked Surface‐Modification Layers
journal, January 2020

  • Wang, Hyun Suk; Oh, Seula; Choi, Junhwan
  • Macromolecular Rapid Communications, Vol. 41, Issue 4
  • DOI: 10.1002/marc.201900514

Homopolymer Nanolithography
journal, July 2017


Directed Self-Assembly of Templatable Block Copolymers by Easily Accessible Magnetic Control
journal, January 2019


Metal Oxide Heterostructure Array via Spatially Controlled–Growth within Block Copolymer Templates
journal, October 2019


Promising Lithography Techniques for Next-Generation Logic Devices
journal, April 2018


Realization of wafer-scale nanogratings with sub-50 nm period through vacancy epitaxy
journal, June 2019


Directed self-assembly of block copolymers for 7 nanometre FinFET technology and beyond
journal, October 2018


Extreme ultraviolet resist materials for sub-7 nm patterning
journal, January 2017

  • Li, Li; Liu, Xuan; Pal, Shyam
  • Chemical Society Reviews, Vol. 46, Issue 16
  • DOI: 10.1039/c7cs00080d

Magnetization switching in high-density magnetic nanodots by a fine-tune sputtering process on a large-area diblock copolymer mask
journal, January 2017

  • Barrera, G.; Celegato, F.; Coïsson, M.
  • Nanoscale, Vol. 9, Issue 43
  • DOI: 10.1039/c7nr04295g

Long-range single domain array of a 5 nm pattern of supramolecules via solvent annealing in a double-sandwich cell
journal, January 2018

  • Kwon, Kiok; Park, Kangho; Jung, Hee-Tae
  • Nanoscale, Vol. 10, Issue 18
  • DOI: 10.1039/c8nr01291a

Polymer–metal coating for high contrast SEM cross sections at the deep nanoscale
journal, January 2018

  • Staaks, Daniel; Olynick, Deirdre L.; Rangelow, Ivo W.
  • Nanoscale, Vol. 10, Issue 48
  • DOI: 10.1039/c8nr06669h

Reactive block copolymers for patterned surface immobilization with sub-30 nm spacing
journal, January 2019

  • Turgut, Hatice; Dingenouts, Nico; Trouillet, Vanessa
  • Polymer Chemistry, Vol. 10, Issue 11
  • DOI: 10.1039/c8py01777h

Nano-confinement of block copolymers in high accuracy topographical guiding patterns: modelling the emergence of defectivity due to incommensurability
journal, January 2018

  • Gottlieb, Steven; Kazazis, Dimitrios; Mochi, Iacopo
  • Soft Matter, Vol. 14, Issue 33
  • DOI: 10.1039/c8sm01045e

Sub-5 nm structured films by hydrogen bonded siloxane liquid crystals and block copolymers
journal, January 2018

  • Nickmans, Koen; Verpaalen, Rob C. P.; Murphy, Jeffrey N.
  • Journal of Materials Chemistry C, Vol. 6, Issue 12
  • DOI: 10.1039/c8tc00627j

Customizing topographical templates for aperiodic nanostructures of block copolymers via inverse design
journal, January 2019

  • Zhang, Runrong; Zhang, Liangshun; Lin, Jiaping
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 15
  • DOI: 10.1039/c9cp00712a

Enhanced microphase separation of thin films of low molecular weight block copolymer by the addition of an ionic liquid
journal, January 2019

  • Li, Dongxue; Zhou, Chun; Xiong, Shisheng
  • Soft Matter, Vol. 15, Issue 48
  • DOI: 10.1039/c9sm02039j

Scattering-mediated absorption from heterogeneous nanoparticle assemblies in diblock copolymer micelles for SERS enhancement
journal, January 2019

  • Zakia, Maulida; Song, Hyerin; Song, Chang Hyeon
  • Journal of Materials Chemistry C, Vol. 7, Issue 17
  • DOI: 10.1039/c9tc00464e

Research Update: Electron beam-based metrology after CMOS
journal, July 2018

  • Liddle, J. A.; Hoskins, B. D.; Vladár, A. E.
  • APL Materials, Vol. 6, Issue 7
  • DOI: 10.1063/1.5038249

Dissipative particle dynamics for directed self-assembly of block copolymers
journal, October 2019

  • Huang, Hejin; Alexander-Katz, Alfredo
  • The Journal of Chemical Physics, Vol. 151, Issue 15
  • DOI: 10.1063/1.5117839

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics
journal, May 2018

  • Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M.
  • Nanotechnology, Vol. 29, Issue 27
  • DOI: 10.1088/1361-6528/aabdc3

Thermal stability of L1 0 -FePt nanodots patterned by self-assembled block copolymer lithography
journal, September 2018


X-ray characterization of contact holes for block copolymer lithography
journal, February 2019

  • Sunday, Daniel F.; Delachat, Florian; Gharbi, Ahmed
  • Journal of Applied Crystallography, Vol. 52, Issue 1
  • DOI: 10.1107/s1600576718017272

PMMA-Assisted Plasma Patterning of Graphene
journal, August 2018

  • Bobadilla, Alfredo D.; Ocola, Leonidas E.; Sumant, Anirudha V.
  • Journal of Nanotechnology, Vol. 2018
  • DOI: 10.1155/2018/8349626

Polarization-insensitive, ultra-broadband, and compact metamaterial-inspired optical absorber via wide-angle and highly efficient performances
journal, January 2018

  • Mehrabi, Mohammad; Rajabalipanah, Hamid; Abdolali, Ali
  • Applied Optics, Vol. 57, Issue 14
  • DOI: 10.1364/ao.57.003693

High‐Fidelity, Sub‐5 nm Patterns from High‐χ Block Copolymer Films with Vapor‐Deposited Ultrathin, Cross‐Linked Surface‐Modification Layers
journal, February 2020

  • Wang, Hyun Suk; Oh, Seula; Choi, Junhwan
  • Macromolecular Rapid Communications, Vol. 41, Issue 4
  • DOI: 10.1002/marc.202070008

Janus Graft Block Copolymers: Design of a Polymer Architecture for Independently Tuned Nanostructures and Polymer Properties
journal, May 2018

  • Guo, Zi-Hao; Le, An N.; Feng, Xunda
  • Angewandte Chemie International Edition, Vol. 57, Issue 28
  • DOI: 10.1002/anie.201802844

Reactive block copolymers for patterned surface immobilization with sub-30 nm spacing
text, January 2019


X-ray characterization of contact holes for block copolymer lithography
text, January 2019


Dissipative Particle Dynamics for Directed Self-Assembly of Block Copolymers
text, January 2019


Rapid Synthesis of Nanoporous Conformal Coatings via Plasma-Enhanced Sequential Infiltration of a Polymer Template
journal, November 2017


Simultaneous fabrication of line and dot dual nanopatterns using miktoarm block copolymer with photocleavable linker
journal, November 2017

  • Choi, Chungryong; Park, Jichoel; Vincent Joseph, Kanniyambatti L.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-02019-9

Realization of wafer-scale nanogratings with sub-50 nm period through vacancy epitaxy
journal, June 2019


Ultra-dense (~20 Tdot/in2) nanoparticle array from an ordered supramolecular dendrimer containing a metal precursor
journal, March 2019


Identifying the nature of surface chemical modification for directed self-assembly of block copolymers
journal, September 2017

  • Evangelio, Laura; Gramazio, Federico; Lorenzoni, Matteo
  • Beilstein Journal of Nanotechnology, Vol. 8
  • DOI: 10.3762/bjnano.8.198