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

Journal Article · · Journal of Polymer Science. Part B, Polymer Physics
DOI:https://doi.org/10.1002/polb.24732· OSTI ID:1490075

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

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357; DE‐AC02‐06CH11357
OSTI ID:
1490075
Alternate ID(s):
OSTI ID: 1472190
Journal Information:
Journal of Polymer Science. Part B, Polymer Physics, Vol. 56, Issue 21; ISSN 0887-6266
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

References (67)

Block Copolymer Lithography journal November 2013
Polymeric Bicontinuous Microemulsions journal August 1997
Nanoporous Membranes Derived from Block Copolymers: From Drug Delivery to Water Filtration journal June 2010
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
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
Block Copolymer Mixtures As Revealed By Neutron Reflectivity journal December 1994
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
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
Dimensional Scaling of Cylinders in Thin Films of Block Copolymer−Homopolymer Ternary Blends journal July 2009
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
The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source journal June 2012
Interfacial Energy-Controlled Top Coats for Gyroid/Cylinder Phase Transitions of Polystyrene- block -polydimethylsiloxane Block Copolymer Thin Films journal May 2017
Block Copolymer Lithography: Merging “Bottom-Up” with “Top-Down” Processes journal December 2005
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
Phase Behavior of Thin Film Blends of Block Copolymers and Homopolymers:  Changes in Domain Dimensions journal February 1999
Swelling of lamellar diblock copolymer by homopolymer: influences of homopolymer concentration and molecular weight journal November 1991
Role of dissimilar interfaces in thin films of cylinder-forming block copolymers journal January 2004
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
Morphology Control in Block Copolymer Films Using Mixed Solvent Vapors journal August 2012
Lamellar Domain Spacings of Diblock Copolymer/Homopolymer Blends and Conformations of Block Chains in Their Microdomains journal September 1997
Ordered morphologies in binary blends of diblock copolymer and homopolymer and characterization of their intermaterial dividing surfaces journal December 1991
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
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
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
Phase Behavior and Dimensional Scaling of Symmetric Block Copolymer−Homopolymer Ternary Blends in Thin Films journal April 2009
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
Static and dynamic scattering from ternary polymer blends: Bicontinuous microemulsions, Lifshitz lines, and amphiphilicity journal April 2001
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
Interfacial properties and phase transitions in ternary symmetric homopolymer–copolymer blends: A dissipative particle dynamics study journal April 2013
Functional block copolymer assemblies responsive to tumor and intracellular microenvironments for site-specific drug delivery and enhanced imaging performance journal January 2013
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
Structural transitions from spherical to nonspherical micelles in blends of poly(styrene-butadiene) diblock copolymer and polystyrene homopolymers journal December 1988
Unexpected Hexagonally Perforated Layer Morphology of PS- b -PMMA Block Copolymer in Supported Thin Film journal January 2006
Experimental study of the surface structure of diblock copolymer films using microscopy and x‐ray scattering journal February 1993
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
Selective Separation of Similarly Sized Proteins with Tunable Nanoporous Block Copolymer Membranes journal December 2012
Sub-10 nm Silicon Nanopillar Fabrication Using Fast and Brushless Thermal Assembly of PS- b -PDMS Diblock Copolymer journal April 2016
Model Bicontinuous Microemulsions in Ternary Homopolymer/Block Copolymer Blends journal June 1999
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
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
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

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