Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films

Abstract

Defects in highly ordered self-assembled block copolymers represent an important roadblock toward the adoption of these materials in a wide range of applications. This work examines the pathways for annihilation of defects in symmetric diblock copolymers in the context of directed assembly using patterned substrates. Past theoretical and computational studies of such systems have predicted minimum free energy pathways that are characteristic of an activated process. However, they have been limited to adjacent dislocations with opposite Burgers vectors. By relying on a combination of advanced sampling techniques and particle-based simulations, this work considers the long-range interaction between dislocation pairs, both on homogeneous and nanopatterned substrates. As illustrated here, these interactions are central to understanding the defect structures that are most commonly found in applications and in experimental studies of directed self-assembly. More specifically, it is shown that, for dislocation dipoles separated by several lamellae, multiple consecutive free energy barriers lead to effective kinetic barriers that are an order of magnitude larger than those originally reported in the literature for tightly bound dislocation pairs. Furthermore, it is also shown that annihilation pathways depend strongly on both the separation between dislocations and their relative position with respect to the substrate guiding stripesmore » used to direct the assembly.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]
+ Show Author Affiliations
  1. Chonnam National Univ., Gwangju (Korea)
  2. Chonnam National Univ., Gwangju (Korea); The Univ. of Chicago, Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States); The Univ. of Texas at San Antonio, San Antonio, TX (United States)
  4. The Univ. of Chicago, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1487452
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 10; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block copolymer; defect annihilation; directed assembly; minimum free energy path; string method

Citation Formats

Hur, Su -Mi, Thapar, Vikram, Ramírez-Hernández, Abelardo, Nealey, Paul F., and de Pablo, Juan J. Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b04202.
Copy to clipboard
Hur, Su -Mi, Thapar, Vikram, Ramírez-Hernández, Abelardo, Nealey, Paul F., & de Pablo, Juan J. Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films. United States. https://doi.org/10.1021/acsnano.8b04202
Copy to clipboard
Hur, Su -Mi, Thapar, Vikram, Ramírez-Hernández, Abelardo, Nealey, Paul F., and de Pablo, Juan J. Tue . "Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films". United States. https://doi.org/10.1021/acsnano.8b04202. https://www.osti.gov/servlets/purl/1487452.
Copy to clipboard
@article{osti_1487452,
title = {Defect Annihilation Pathways in Directed Assembly of Lamellar Block Copolymer Thin Films},
author = {Hur, Su -Mi and Thapar, Vikram and Ramírez-Hernández, Abelardo and Nealey, Paul F. and de Pablo, Juan J.},
abstractNote = {Defects in highly ordered self-assembled block copolymers represent an important roadblock toward the adoption of these materials in a wide range of applications. This work examines the pathways for annihilation of defects in symmetric diblock copolymers in the context of directed assembly using patterned substrates. Past theoretical and computational studies of such systems have predicted minimum free energy pathways that are characteristic of an activated process. However, they have been limited to adjacent dislocations with opposite Burgers vectors. By relying on a combination of advanced sampling techniques and particle-based simulations, this work considers the long-range interaction between dislocation pairs, both on homogeneous and nanopatterned substrates. As illustrated here, these interactions are central to understanding the defect structures that are most commonly found in applications and in experimental studies of directed self-assembly. More specifically, it is shown that, for dislocation dipoles separated by several lamellae, multiple consecutive free energy barriers lead to effective kinetic barriers that are an order of magnitude larger than those originally reported in the literature for tightly bound dislocation pairs. Furthermore, it is also shown that annihilation pathways depend strongly on both the separation between dislocations and their relative position with respect to the substrate guiding stripes used to direct the assembly.},
doi = {10.1021/acsnano.8b04202},
journal = {ACS Nano},
number = 10,
volume = 12,
place = {United States},
year = {2018},
month = {9}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsnano.8b04202
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

Fig. 1 Fig. 1: MFEP between a dislocation dipole separated by two periods and defectfree lamellar structures. (A) Free-energy difference, $∆F$ , as a function of reaction coordinate, $α$. (B) Several representative morphologies (top-down and bottom-up views) along the pathway. The top views for the initial and final morphologies of the equilibriummore » pathway are also shown. (C) Three-dimensional view of the morphology corresponding to the first (t1) and the second transition state (t2).« less
All figures and tables (6 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

Block copolymers and conventional lithography
journal, September 2006

Block Copolymer Lithography: Periodic Arrays of 1011 Holes in 1 Square Centimeter
journal, May 1997

Polymers on Nanoperiodic, Heterogeneous Surfaces
journal, March 1999

Enabling nanotechnology with self assembled block copolymer patterns
journal, October 2003

Block Copolymer Based Nanostructures: Materials, Processes, and Applications to Electronics
journal, January 2010

  • Kim, Ho-Cheol; Park, Sang-Min; Hinsberg, William D.
  • Chemical Reviews, Vol. 110, Issue 1
  • DOI: 10.1021/cr900159v

Block Copolymer Lithography
journal, November 2013

  • Bates, Christopher M.; Maher, Michael J.; Janes, Dustin W.
  • Macromolecules, Vol. 47, Issue 1, p. 2-12
  • DOI: 10.1021/ma401762n

Beyond native block copolymer morphologies
journal, January 2017

  • Doerk, Gregory S.; Yager, Kevin G.
  • Molecular Systems Design & Engineering, Vol. 2, Issue 5
  • DOI: 10.1039/C7ME00069C

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

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

Evolution of Block Copolymer Lithography to Highly Ordered Square Arrays
journal, October 2008

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

Design rules for self-assembled block copolymer patterns using tiled templates
journal, February 2014

  • Chang, Jae-Byum; Choi, Hong Kyoon; Hannon, Adam F.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4305

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

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

Graphoepitaxy of Spherical Domain Block Copolymer Films
journal, August 2001

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

Electric field directed self-assembly of block copolymers for rapid formation of large-area complex nanopatterns
journal, January 2017

  • Jeon, Hyun Uk; Jin, Hyeong Min; Kim, Ju Young
  • Molecular Systems Design & Engineering, Vol. 2, Issue 5
  • DOI: 10.1039/C7ME00067G

Directing block copolymer self-assembly with permanent magnets: photopatterning microdomain alignment and generating oriented nanopores
journal, January 2017

  • Gopinadhan, Manesh; Choo, Youngwoo; Mahajan, Lalit H.
  • Molecular Systems Design & Engineering, Vol. 2, Issue 5
  • DOI: 10.1039/C7ME00070G

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

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

Integration of Density Multiplication in the Formation of Device-Oriented Structures by Directed Assembly of Block Copolymer-Homopolymer Blends
journal, April 2010

  • Liu, Guoliang; Thomas, Carla S.; Craig, Gordon S. W.
  • Advanced Functional Materials, Vol. 20, Issue 8
  • DOI: 10.1002/adfm.200902229

Sub-10-nm patterning via directed self-assembly of block copolymer films with a vapour-phase deposited topcoat
journal, March 2017

  • Suh, Hyo Seon; Kim, Do Han; Moni, Priya
  • Nature Nanotechnology, Vol. 12, Issue 6
  • DOI: 10.1038/nnano.2017.34

Mechanisms of Ordering in Striped Patterns
journal, November 2000

Defects in the Self-Assembly of Block Copolymers and Their Relevance for Directed Self-Assembly
journal, July 2015

Anomalous Rapid Defect Annihilation in Self-Assembled Nanopatterns by Defect Melting
journal, January 2015

  • Kim, Bong Hoon; Park, So Jung; Jin, Hyeong Min
  • Nano Letters, Vol. 15, Issue 2
  • DOI: 10.1021/nl5042935

Simulation of Defect Reduction in Block Copolymer Thin Films by Solvent Annealing
journal, December 2014

  • Hur, Su-Mi; Khaira, Gurdaman S.; Ramírez-Hernández, Abelardo
  • ACS Macro Letters, Vol. 4, Issue 1
  • DOI: 10.1021/mz500705q

Flash Light Millisecond Self-Assembly of High χ Block Copolymers for Wafer-Scale Sub-10 nm Nanopatterning
journal, June 2017

  • Jin, Hyeong Min; Park, Dae Yong; Jeong, Seong-Jun
  • Advanced Materials, Vol. 29, Issue 32
  • DOI: 10.1002/adma.201700595

Defect Structure in Thin Films of a Lamellar Block Copolymer Self-Assembled on Neutral Homogeneous and Chemically Nanopatterned Surfaces
journal, August 2006

  • Kim, Sang Ouk; Kim, Bong Hoon; Kim, Kwanghyon
  • Macromolecules, Vol. 39, Issue 16
  • DOI: 10.1021/ma060087u

Free Energy of Defects in Ordered Assemblies of Block Copolymer Domains
journal, February 2012

  • Nagpal, Umang; Müller, Marcus; Nealey, Paul F.
  • ACS Macro Letters, Vol. 1, Issue 3
  • DOI: 10.1021/mz200245s

Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects
journal, July 2012

  • Takahashi, Hassei; Laachi, Nabil; Delaney, Kris T.
  • Macromolecules, Vol. 45, Issue 15
  • DOI: 10.1021/ma300993x

Defect Removal in the Course of Directed Self-Assembly is Facilitated in the Vicinity of the Order-Disorder Transition
journal, October 2014

Thermodynamic and kinetic aspects of defectivity in directed self-assembly of cylinder-forming diblock copolymers in laterally confining thin channels
journal, April 2014

  • Kim, Bongkeun; Laachi, Nabil; Delaney, Kris T.
  • Journal of Applied Polymer Science, Vol. 131, Issue 24
  • DOI: 10.1002/app.40790

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
  • DOI: 10.1073/pnas.1508225112

Real-Time Atomic Force Microscopy Imaging of Block Copolymer Directed Self Assembly
journal, November 2017

Stable and unstable phases of a diblock copolymer melt
journal, April 1994

Continuum models for directed self-assembly
journal, January 2018

  • Müller, Marcus; Orozco Rey, Juan Carlos
  • Molecular Systems Design & Engineering, Vol. 3, Issue 2
  • DOI: 10.1039/C7ME00109F

Monte Carlo Simulation of Coarse Grain Polymeric Systems
journal, May 2009

Simulations of theoretically informed coarse grain models of polymeric systems
journal, January 2010

  • Detcheverry, François A.; Pike, Darin Q.; Nealey, Paul F.
  • Faraday Discuss., Vol. 144
  • DOI: 10.1039/B902283J

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
  • DOI: 10.1021/ma902332h

Design of surface patterns with optimized thermodynamic driving forces for the directed self-assembly of block copolymers in lithographic applications
journal, January 2017

  • Garner, Grant P.; Rincon Delgadillo, Paulina; Gronheid, Roel
  • Molecular Systems Design & Engineering, Vol. 2, Issue 5
  • DOI: 10.1039/C7ME00028F

String method for the study of rare events
journal, August 2002

Solvent coarse-graining and the string method applied to the hydrophobic collapse of a hydrated chain
journal, August 2007

  • Miller, T. F.; Vanden-Eijnden, E.; Chandler, D.
  • Proceedings of the National Academy of Sciences, Vol. 104, Issue 37
  • DOI: 10.1073/pnas.0705830104

Simplified and improved string method for computing the minimum energy paths in barrier-crossing events
journal, April 2007

  • E., Weinan; Ren, Weiqing; Vanden-Eijnden, Eric
  • The Journal of Chemical Physics, Vol. 126, Issue 16
  • DOI: 10.1063/1.2720838

Nucleation of Ordered Phases in Block Copolymers
journal, April 2010

Minimum Energy Path to Membrane Pore Formation and Rupture
journal, April 2011

Transition Path from Two Apposed Membranes to a Stalk Obtained by a Combination of Particle Simulations and String Method
journal, May 2012

    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Shear-solvo defect annihilation of diblock copolymer thin films over a large area
    journal, June 2019

    Combining double patterning with self-assembled block copolymer lamellae to fabricate 10.5 nm full-pitch line/space patterns
    journal, August 2019

    Ionic conductivity and counterion condensation in nanoconfined polycation and polyanion brushes prepared from block copolymer templates
    journal, January 2019

    • Arges, Christopher G.; Li, Ke; Zhang, Le
    • Molecular Systems Design & Engineering, Vol. 4, Issue 2
    • DOI: 10.1039/c8me00081f
      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Fig. 1 (p. 7)figure
      Fig. 2 (p. 8)figure
      Fig. 3 (p. 11)figure
      Fig. 4 (p. 12)figure
      Fig. 5 (p. 13)figure
      Fig. 6 (p. 16)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: