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Title: Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends

Abstract

ABSTRACT The thin film phase behavior of ternary blends consisting of symmetric poly(styrene) (PS)‐ b ‐poly(dimethylsiloxane)(PDMS), PS, and PDMS was investigated using X‐ray reflectivity (XRR) and atomic force microscopy (AFM). This system is strongly segregated, and the homopolymers are approximately the same length as the corresponding blocks of the copolymer. The XRR and AFM data are used to quantify changes in domain spacing ( L ) and morphology evolution with increasing homopolymer content (Φ H ). In 100 nm thick films, from Φ H = 0 to 0.20, the system maintains a perfect parallel lamellar structure and domains swell as predicted based on theory; however, from Φ H = 0.30 to 0.50, a morphology transition to a “dot pattern” morphology (tentatively identified as perforated lamellae) and mixed morphologies were observed before macrophase separation. In thicker films, dot patterns were observed for a broad range of Φ H before macrophase separation. The absence of the bicontinuous microemulsion phase reported for bulk blends and thin films of perpendicular lamellae and the presence of dot patterns/perforated lamellae are attributed to preferential migration of the PDMS homopolymer to the wetting layers located at the substrate andmore » free air interfaces, which leads to an asymmetric composition within the film and morphology transition. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56 , 1443–1451« less

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [1]
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  1. Tulane Univ., New Orleans, LA (United States)
  2. 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)
OSTI Identifier:
1490075
Alternate Identifier(s):
OSTI ID: 1472190
Grant/Contract Number:  
AC02-06CH11357; DE‐AC02‐06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Polymer Science. Part B, Polymer Physics
Additional Journal Information:
Journal Volume: 56; Journal Issue: 21; Journal ID: ISSN 0887-6266
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block copolymer blend; domain spacing; perforated lamellae; thin film morphology

Citation Formats

Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., and Albert, Julie N. L. Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends. United States: N. p., 2018. Web. doi:10.1002/polb.24732.
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Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., & Albert, Julie N. L. Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends. United States. https://doi.org/10.1002/polb.24732
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Uddin, Md Fakar, Jiang, Zhang, Raymond, Andrew, Goodson, Amy D., Lwoya, Baraka S., and Albert, Julie N. L. Sun . "Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends". United States. https://doi.org/10.1002/polb.24732. https://www.osti.gov/servlets/purl/1490075.
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@article{osti_1490075,
title = {Thin film confinement reduces compatibility in symmetric ternary block copolymer/homopolymer blends},
author = {Uddin, Md Fakar and Jiang, Zhang and Raymond, Andrew and Goodson, Amy D. and Lwoya, Baraka S. and Albert, Julie N. L.},
abstractNote = {ABSTRACT The thin film phase behavior of ternary blends consisting of symmetric poly(styrene) (PS)‐ b ‐poly(dimethylsiloxane)(PDMS), PS, and PDMS was investigated using X‐ray reflectivity (XRR) and atomic force microscopy (AFM). This system is strongly segregated, and the homopolymers are approximately the same length as the corresponding blocks of the copolymer. The XRR and AFM data are used to quantify changes in domain spacing ( L ) and morphology evolution with increasing homopolymer content (Φ H ). In 100 nm thick films, from Φ H = 0 to 0.20, the system maintains a perfect parallel lamellar structure and domains swell as predicted based on theory; however, from Φ H = 0.30 to 0.50, a morphology transition to a “dot pattern” morphology (tentatively identified as perforated lamellae) and mixed morphologies were observed before macrophase separation. In thicker films, dot patterns were observed for a broad range of Φ H before macrophase separation. The absence of the bicontinuous microemulsion phase reported for bulk blends and thin films of perpendicular lamellae and the presence of dot patterns/perforated lamellae are attributed to preferential migration of the PDMS homopolymer to the wetting layers located at the substrate and free air interfaces, which leads to an asymmetric composition within the film and morphology transition. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56 , 1443–1451},
doi = {10.1002/polb.24732},
journal = {Journal of Polymer Science. Part B, Polymer Physics},
number = 21,
volume = 56,
place = {United States},
year = {Sun Sep 23 00:00:00 EDT 2018},
month = {Sun Sep 23 00:00:00 EDT 2018}
}
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https://doi.org/10.1002/polb.24732
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Figures / Tables:

Figure 1 Figure 1: X-ray reflectivity (XRR) profiles as a function of $Q$$Z$ (nm -1 ), through-film scattering length density (SLD) profiles used to calculate the reflectivity profile, and AFM height images(scale bar = 10 $μ$m and height color scale = 100 nm) of representative PS-b-PDMS and ternary blend films. On themore » XRR profiles, the open colored circles represent the measured data points and solid lines represent the calculated reflectivity profile. Three morphological regimes are noted: (a) from $Փ$$H$ = 0 to 0.20 (red box), parallel lamellae; (b) from $Փ$$H$ = 0.30 to 0.50 (blue box), morphology transition; (c) from $Փ$$H$ =0.60 to 0.80 (green box), macrophase separated.« less
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Works referenced in this record:

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

Polymeric Bicontinuous Microemulsions
journal, August 1997

Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration
journal, June 2010

  • Jackson, Elizabeth A.; Hillmyer, Marc A.
  • ACS Nano, Vol. 4, Issue 7
  • DOI: 10.1021/nn1014006

Controlling Polymer-Surface Interactions with Random Copolymer Brushes
journal, March 1997

Theory of Microphase Separation in Block Copolymers
journal, November 1980

Elastic properties of a diblock copolymer monolayer and their relevance to bicontinuous microemulsion
journal, March 1999

  • Matsen, M. W.
  • The Journal of Chemical Physics, Vol. 110, Issue 9
  • DOI: 10.1063/1.478349

Lamellar Orientation in Thin, Supported Diblock Copolymer Films:  Strong Segregation Theory
journal, May 2004

Generation of Monolayer Gradients in Surface Energy and Surface Chemistry for Block Copolymer Thin Film Studies
journal, November 2009

  • Albert, Julie N. L.; Baney, Michael J.; Stafford, Christopher M.
  • ACS Nano, Vol. 3, Issue 12
  • DOI: 10.1021/nn900750w

Block Copolymer Mixtures As Revealed By Neutron Reflectivity
journal, December 1994

  • Mayes, A. M.; Russell, T. P.; Deline, V. R.
  • Macromolecules, Vol. 27, Issue 25
  • DOI: 10.1021/ma00103a030

Self-assembly of block copolymer thin films
journal, June 2010

Orientation-Controlled Self-Assembled Nanolithography Using a Polystyrene−Polydimethylsiloxane Block Copolymer
journal, July 2007

Isothermal morphology diagrams for binary blends of diblock copolymer and homopolymer
journal, May 1992

  • Winey, Karen I.; Thomas, Edwin L.; Fetters, Lewis J.
  • Macromolecules, Vol. 25, Issue 10
  • DOI: 10.1021/ma00036a014

Ordered Structures and Phase Transitions in Mixtures of a Polystyrene/Polyisoprene Block Copolymer with the Corresponding Homopolymers in Thin Films and in Bulk
journal, May 2004

  • Mykhaylyk, Tetyana A.; Mykhaylyk, Oleksandr O.; Collins, Stephen
  • Macromolecules, Vol. 37, Issue 9
  • DOI: 10.1021/ma035758s

Dimensional Scaling of Cylinders in Thin Films of Block Copolymer−Homopolymer Ternary Blends
journal, July 2009

  • Stuen, Karl O.; Thomas, Carla S.; Liu, Guoliang
  • Macromolecules, Vol. 42, Issue 14
  • DOI: 10.1021/ma900520v

Local Control of Microdomain Orientation in Diblock Copolymer Thin Films with Electric Fields
journal, August 1996

Polymer-Polymer Phase Behavior
journal, February 1991

Substrate Surface Energy Dependent Morphology and Dewetting in an ABC Triblock Copolymer Film
journal, March 2007

  • Epps, Thomas H.; DeLongchamp, Dean M.; Fasolka, Michael J.
  • Langmuir, Vol. 23, Issue 6
  • DOI: 10.1021/la062707q

The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source
journal, June 2012

  • Jiang, Zhang; Li, Xuefa; Strzalka, Joseph
  • Journal of Synchrotron Radiation, Vol. 19, Issue 4
  • DOI: 10.1107/S0909049512022017

Interfacial Energy-Controlled Top Coats for Gyroid/Cylinder Phase Transitions of Polystyrene- block -polydimethylsiloxane Block Copolymer Thin Films
journal, May 2017

  • Ryu, In Hyu; Kim, Yong Joo; Jung, Yeon Sik
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 20
  • DOI: 10.1021/acsami.7b02910

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

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990

Phase Behavior of Symmetric Ternary Block Copolymer-Homopolymer Blends in Thin Films and on Chemically Patterned Surfaces
journal, October 2006

Block copolymer self-assembly for nanophotonics
journal, January 2015

  • Stefik, Morgan; Guldin, Stefan; Vignolini, Silvia
  • Chemical Society Reviews, Vol. 44, Issue 15
  • DOI: 10.1039/C4CS00517A

Phase Behavior of Thin Film Blends of Block Copolymers and Homopolymers:  Changes in Domain Dimensions
journal, February 1999

  • Orso, Keith A.; Green, Peter F.
  • Macromolecules, Vol. 32, Issue 4
  • DOI: 10.1021/ma981356m

Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight
journal, November 1991

  • Winey, Karen I.; Thomas, Edwin L.; Fetters, Lewis J.
  • Macromolecules, Vol. 24, Issue 23
  • DOI: 10.1021/ma00023a020

Role of dissimilar interfaces in thin films of cylinder-forming block copolymers
journal, January 2004

  • Lyakhova, K. S.; Sevink, G. J. A.; Zvelindovsky, A. V.
  • The Journal of Chemical Physics, Vol. 120, Issue 2
  • DOI: 10.1063/1.1632475

Effect of Architecture on the Phase Behavior of AB-Type Block Copolymer Melts
journal, February 2012

Rapid Ordering in “Wet Brush” Block Copolymer/Homopolymer Ternary Blends
journal, October 2016

Phase equilibria in copolymer/homopolymer ternary blends: Molecular weight effects
journal, August 1990

  • Broseta, Daniel; Fredrickson, Glenn H.
  • The Journal of Chemical Physics, Vol. 93, Issue 4
  • DOI: 10.1063/1.458877

Morphology Control in Block Copolymer Films Using Mixed Solvent Vapors
journal, August 2012

  • Gotrik, Kevin W.; Hannon, Adam F.; Son, Jeong Gon
  • ACS Nano, Vol. 6, Issue 9
  • DOI: 10.1021/nn302641z

Lamellar Domain Spacings of Diblock Copolymer/Homopolymer Blends and Conformations of Block Chains in Their Microdomains
journal, September 1997

  • Torikai, Naoya; Takabayashi, Naomi; Noda, Ichiro
  • Macromolecules, Vol. 30, Issue 19
  • DOI: 10.1021/ma961936o

Ordered morphologies in binary blends of diblock copolymer and homopolymer and characterization of their intermaterial dividing surfaces
journal, December 1991

  • Winey, Karen I.; Thomas, Edwin L.; Fetters, Lewis J.
  • The Journal of Chemical Physics, Vol. 95, Issue 12
  • DOI: 10.1063/1.461164

GenX : an extensible X-ray reflectivity refinement program utilizing differential evolution
journal, November 2007

Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition
journal, December 1995

  • Khandpur, Ashish K.; Foerster, Stephan; Bates, Frank S.
  • Macromolecules, Vol. 28, Issue 26
  • DOI: 10.1021/ma00130a012

Phase Behavior of Block Copolymer/Homopolymer Blends
journal, August 1995

Edge profile of relief 2D domains at the free surface of smectic copolymer thin films
journal, March 1992

Reducing Block Copolymer Interfacial Widths through Polymer Additives
journal, January 2015

  • Sunday, Daniel F.; Kline, R. Joseph
  • Macromolecules, Vol. 48, Issue 3
  • DOI: 10.1021/ma502015u

Block Copolymer Membranes for Aqueous Solution Applications
journal, March 2016

Growth of two dimensional domains in copolymer thin films
journal, January 1990

Nanostructured Block Copolymers for Proton Exchange Membrane Fuel Cells
journal, December 2015

  • Lwoya, Baraka S.; Albert, Julie N. L.
  • Energy and Environment Focus, Vol. 4, Issue 4
  • DOI: 10.1166/eef.2015.1179

Phase Behavior and Dimensional Scaling of Symmetric Block Copolymer−Homopolymer Ternary Blends in Thin Films
journal, April 2009

  • Liu, Guoliang; Stoykovich, Mark P.; Ji, Shengxiang
  • Macromolecules, Vol. 42, Issue 8
  • DOI: 10.1021/ma802773h

Solvent-Vapor-Induced Tunability of Self-Assembled Block Copolymer Patterns
journal, June 2009

Localization of a homopolymer dissolved in a lamellar structure of a block copolymer studied by small-angle neutron scattering
journal, November 1993

  • Matsushita, Yushu; Torikai, Naoya; Mogi, Yasuhiro
  • Macromolecules, Vol. 26, Issue 24
  • DOI: 10.1021/ma00076a007

Static and dynamic scattering from ternary polymer blends: Bicontinuous microemulsions, Lifshitz lines, and amphiphilicity
journal, April 2001

  • Morkved, Terry L.; Stepanek, Petr; Krishnan, Kasiraman
  • The Journal of Chemical Physics, Vol. 114, Issue 16
  • DOI: 10.1063/1.1357800

Fabrication of micellar nanoparticles for drug delivery through the self-assembly of block copolymers
journal, September 2010

Morphological studies of micelle formation in block copolymer/homopolymer blends
journal, May 1989

  • Kinning, David J.; Thomas, Edwin L.; Fetters, Lewis J.
  • The Journal of Chemical Physics, Vol. 90, Issue 10
  • DOI: 10.1063/1.456388

Enhancement in the Orientation of the Microdomain in Block Copolymer Thin Films upon the Addition of Homopolymer
journal, March 2004

Homopolymer distributions in ordered block copolymers
journal, November 1992

  • Mayes, A. M.; Russell, T. P.; Satija, S. K.
  • Macromolecules, Vol. 25, Issue 24
  • DOI: 10.1021/ma00050a022

Structural transitions from spherical to nonspherical micelles in blends of poly(styrene-butadiene) diblock copolymer and polystyrene homopolymers
journal, December 1988

  • Kinning, David J.; Winey, Karen I.; Thomas, Edwin L.
  • Macromolecules, Vol. 21, Issue 12
  • DOI: 10.1021/ma00190a027

Unexpected Hexagonally Perforated Layer Morphology of PS- b -PMMA Block Copolymer in Supported Thin Film
journal, January 2006

  • Park, Insun; Park, Soojin; Park, Hae-Woong
  • Macromolecules, Vol. 39, Issue 1
  • DOI: 10.1021/ma0515937

Experimental study of the surface structure of diblock copolymer films using microscopy and x‐ray scattering
journal, February 1993

  • Cai, Zhong‐hou; Huang, Kegang; Montano, P. A.
  • The Journal of Chemical Physics, Vol. 98, Issue 3
  • DOI: 10.1063/1.464165

50th Anniversary Perspective : Functional Nanoparticles from the Solution Self-Assembly of Block Copolymers
journal, April 2017

Reversible Morphology Control in Block Copolymer Films via Solvent Vapor Processing: An in Situ GISAXS Study
journal, May 2010

  • Paik, Marvin Y.; Bosworth, Joan K.; Smilges, Detlef-M.
  • Macromolecules, Vol. 43, Issue 9
  • DOI: 10.1021/ma902646t

Selective Separation of Similarly Sized Proteins with Tunable Nanoporous Block Copolymer Membranes
journal, December 2012

  • Qiu, Xiaoyan; Yu, Haizhou; Karunakaran, Madhavan
  • ACS Nano, Vol. 7, Issue 1
  • DOI: 10.1021/nn305073e

Sub-10 nm Silicon Nanopillar Fabrication Using Fast and Brushless Thermal Assembly of PS- b -PDMS Diblock Copolymer
journal, April 2016

  • Garnier, Jérôme; Arias-Zapata, Javier; Marconot, Olivier
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 15
  • DOI: 10.1021/acsami.6b01255

Model Bicontinuous Microemulsions in Ternary Homopolymer/Block Copolymer Blends
journal, June 1999

  • Hillmyer, Marc A.; Maurer, Wayne W.; Lodge, Timothy P.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 23
  • DOI: 10.1021/jp990089z

Islands and holes on the free surface of thin diblock copolymer films. I. Characteristics of formation and growth
journal, January 1990

Phase Behavior of Mixtures of Block Copolymer and Homopolymers in Thin Films and Bulk
journal, May 2003

  • Jeong, Unyong; Ryu, Du Yeol; Kho, Dong Han
  • Macromolecules, Vol. 36, Issue 10
  • DOI: 10.1021/ma034179k

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

Influence of Conformational Asymmetry on the Phase Behavior of Ternary Homopolymer/Block Copolymer Blends around the Bicontinuous Microemulsion Channel
journal, March 2006

  • Zhou, Ning; Lodge, Timothy P.; Bates, Frank S.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 9
  • DOI: 10.1021/jp055704f

Combinatorial Study of Surface Pattern Formation in Thin Block Copolymer Films
journal, June 2001

Interference microscopy on thin diblock copolymer films
journal, January 1990

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

Supramolecular Materials via Block Copolymer Self-Assembly
journal, August 2001

Combinatorial Study of Surface Pattern Formation in Thin Block Copolymer Films
text, January 2001

  • Amis, Eric J.; Douglas, Jack F.; Karim, Alamgir
  • The American Physical Society
  • DOI: 10.17877/de290r-10250
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    Works referencing / citing this record:

    Nanostructure stability and swelling of ternary block copolymer/homopolymer blends: A direct comparison between dissipative particle dynamics and experiment
    journal, April 2019

    • Goodson, Amy D.; Liu, Guoliang; Rick, Maxwell S.
    • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 12
    • DOI: 10.1002/polb.24834
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      Figure 1 (p. 11)figure
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      Figure 3 (p. 15)figure
      Figure 4 (p. 17)figure
      Figure 5 (p. 18)figure
      Table S1 (p. 29)table
      Table S2 (p. 29)table
      Figure S1 (p. 30)figure
      Figure S1 (p. 31)figure
      Figure S1 (p. 32)figure
      Figure S2 (p. 33)figure
      Figure S3 (p. 34)figure
      Figure S4 (p. 35)figure
      Figure S5 (p. 36)figure
      Figure S6 (p. 37)figure
      Table S3 (p. 38)table
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