Ordering of lamellar block copolymers on oxidized silane coatings

Mahadevapuram, Nikhila; Mitra, Indranil; Sridhar, Shyam; Strzalka, Joseph; Stein, Gila E.

doi:10.1016/j.eurpolymj.2016.01.010

Title: Ordering of lamellar block copolymers on oxidized silane coatings

Abstract

Thin films of lamellar poly(styrene-b-methyl methacrylate) (PS-PMMA) block copolymers are widely investigated for surface patterning. These materials can generate dense arrays of nanoscale lines when the lamellar domains are oriented perpendicular to the substrate. To stabilize this preferred domain orientation, we tuned the substrate surface energy using oxidation of hydrophobic silane coatings. This simple approach is effective for a broad range of PS-PMMA film thicknesses when the oxidation time is optimized, which demonstrates that the substrate coating is energetically neutral with respect to PS and PMMA segments. The lamellar films are characterized by high densities of defects that exhibit a strong dependence on film thickness: in-plane topological defects disrupt the lateral order in ultrathin films, while lamellar domains in thick films can bend and tilt to large misorientation angles. As a result, the types and densities of these defects are similar to those observed with other classes of neutral substrate coatings, such as random copolymer brushes, which demonstrates that oxidized silanes can be used to control PS-PMMA self assembly in thin films.

Authors:

Mahadevapuram, Nikhila ^[1]; Mitra, Indranil ^[1]; Sridhar, Shyam ^[1]; Strzalka, Joseph ^[2]; Stein, Gila E. ^[1]

Univ. of Houston, Houston, TX (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: Sat Jan 02 00:00:00 EST 2016

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: National Science Foundation (NSF); USDOE Office of Science (SC)

OSTI Identifier:: 1338963

Alternate Identifier(s):: OSTI ID: 1341127

Grant/Contract Number:: AC02-06CH11357; DMR-1151468

Resource Type:: Accepted Manuscript

Journal Name:: European Polymer Journal

Additional Journal Information:: Journal Volume: 75; Journal Issue: C; Journal ID: ISSN 0014-3057

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; block copolymer; GISAXS; lithography; patterning; silane; thin film

Citation Formats


                    Mahadevapuram, Nikhila, Mitra, Indranil, Sridhar, Shyam, Strzalka, Joseph, and Stein, Gila E. Ordering of lamellar block copolymers on oxidized silane coatings.  United States: N. p., 2016. 
Web.  doi:10.1016/j.eurpolymj.2016.01.010.

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                    Mahadevapuram, Nikhila, Mitra, Indranil, Sridhar, Shyam, Strzalka, Joseph, & Stein, Gila E. Ordering of lamellar block copolymers on oxidized silane coatings.  United States.  https://doi.org/10.1016/j.eurpolymj.2016.01.010

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                    Mahadevapuram, Nikhila, Mitra, Indranil, Sridhar, Shyam, Strzalka, Joseph, and Stein, Gila E. Sat .  
"Ordering of lamellar block copolymers on oxidized silane coatings".  United States.  https://doi.org/10.1016/j.eurpolymj.2016.01.010.  https://www.osti.gov/servlets/purl/1338963.

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@article{osti_1338963,

  title        = {Ordering of lamellar block copolymers on oxidized silane coatings},

  author       = {Mahadevapuram, Nikhila and Mitra, Indranil and Sridhar, Shyam and Strzalka, Joseph and Stein, Gila E.},

  abstractNote = {Thin films of lamellar poly(styrene-b-methyl methacrylate) (PS-PMMA) block copolymers are widely investigated for surface patterning. These materials can generate dense arrays of nanoscale lines when the lamellar domains are oriented perpendicular to the substrate. To stabilize this preferred domain orientation, we tuned the substrate surface energy using oxidation of hydrophobic silane coatings. This simple approach is effective for a broad range of PS-PMMA film thicknesses when the oxidation time is optimized, which demonstrates that the substrate coating is energetically neutral with respect to PS and PMMA segments. The lamellar films are characterized by high densities of defects that exhibit a strong dependence on film thickness: in-plane topological defects disrupt the lateral order in ultrathin films, while lamellar domains in thick films can bend and tilt to large misorientation angles. As a result, the types and densities of these defects are similar to those observed with other classes of neutral substrate coatings, such as random copolymer brushes, which demonstrates that oxidized silanes can be used to control PS-PMMA self assembly in thin films.},

  doi          = {10.1016/j.eurpolymj.2016.01.010},

  journal      = {European Polymer Journal},

  number       = C,

  volume       = 75,

  place        = {United States},

  year         = {Sat Jan 02 00:00:00 EST 2016},

  month        = {Sat Jan 02 00:00:00 EST 2016}

}

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Works referencing / citing this record:

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journal, August 2016

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Journal of Physics: Condensed Matter, Vol. 28, Issue 40
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Title: Ordering of lamellar block copolymers on oxidized silane coatings

Abstract

Citation Formats

Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement journal, February 2015

A Highly Efficient Sensor Platform Using Simply Manufactured Nanodot Patterned Substrates journal, August 2015

Block Copolymer Lithography journal, November 2013

Directed self-assembly of block copolymers for nanocircuitry fabrication journal, January 2015

Block Copolymer Nanolithography: Translation of Molecular Level Control to Nanoscale Patterns journal, July 2009

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

Consequences of Surface Neutralization in Diblock Copolymer Thin Films journal, October 2013

A Generalized Approach to the Modification of Solid Surfaces journal, April 2005

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

Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains journal, December 2008

Interplay of surface chemical composition and film thickness on graphoepitaxial assembly of asymmetric block copolymers journal, January 2013

Ultrathin Random Copolymer-Grafted Layers for Block Copolymer Self-Assembly journal, May 2015

Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers journal, August 2011

Perpendicular orientation of microdomains in PS-b-PMMA thin films on the PS brushed substrates journal, January 2011

Engineering Silicon Oxide Surfaces Using Self-Assembled Monolayers journal, October 2005

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

Controlled vapor deposition approach to generating substrate surface energy/chemistry gradients journal, June 2011

Manipulating Nanoscale Morphologies in Cylinder-Forming Poly(styrene- b -isoprene- b -styrene) Thin Films Using Film Thickness and Substrate Surface Chemistry Gradients journal, February 2013

Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates journal, July 2003

Easy Orientation of Diblock Copolymers on Self-Assembled Monolayers Using UV Irradiation journal, November 2009

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

Calculation of interfacial tension in polymer systems journal, January 1971

Polar and Nonpolar Interactions in Adhesion journal, January 1973

Surface and interfacial tensions of polymer melts. II. Poly(methyl methacrylate), poly(n-butyl methacrylate), and polystyrene journal, February 1970

Forces involved in the adhesive process journal, February 1970

Interfacial Segregation in Disordered Block Copolymers: Effect of Tunable Surface Potentials journal, July 1997

Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions journal, July 2009

Polymer surface modification by plasmas and photons journal, May 1996

Interface and surface effects on the glass-transition temperature in thin polymer films journal, January 1994

Dependence of the Glass Transition Temperature of Polymer Films on Interfacial Energy and Thickness journal, July 2001

Extraordinary elevation of the glass transition temperature of thin polymer films grafted to silicon oxide substrates journal, December 2001

Mechanisms of Ordering in Striped Patterns journal, November 2000

Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers journal, July 2005

Observation of surface corrugation-induced alignment of lamellar microdomains in PS-b-PMMA thin films journal, January 2009

Symmetric Diblock Copolymer Thin Films on Rough Substrates. Kinetics and Structure Formation in Pure Block Copolymer Thin Films journal, March 2005

Processing Approaches for the Defect Engineering of Lamellar-Forming Block Copolymers in Thin Films journal, December 2013

Probing surface and interface morphology with Grazing Incidence Small Angle X-Ray Scattering journal, August 2009

Layering Transitions in Thin Films of Spherical-Domain Block Copolymers journal, April 2007

Impact of Film Thickness on the Morphology of Mesoporous Carbon Films Using Organic−Organic Self-Assembly journal, May 2011

Surface versus Confinement Induced Morphology Transition in Triblock Copolymer Films: A Grazing Incidence Small Angle Neutron Scattering Investigation journal, October 2006

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Directed Self-Assembly of Lamellar Copolymers: Effects of Interfacial Interactions on Domain Shape journal, October 2012

Controlling interfacial interactions for directed self assembly of block copolymers journal, May 2014

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Percolating Transport and the Conductive Scaling Relationship in Lamellar Block Copolymers under Confinement
journal, February 2015

A Highly Efficient Sensor Platform Using Simply Manufactured Nanodot Patterned Substrates
journal, August 2015

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journal, November 2013

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journal, January 2015

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journal, July 2009

Polarity-Switching Top Coats Enable Orientation of Sub-10-nm Block Copolymer Domains
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A Generalized Approach to the Modification of Solid Surfaces
journal, April 2005

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

Effect of Composition of Substrate-Modifying Random Copolymers on the Orientation of Symmetric and Asymmetric Diblock Copolymer Domains
journal, December 2008

Interplay of surface chemical composition and film thickness on graphoepitaxial assembly of asymmetric block copolymers
journal, January 2013

Ultrathin Random Copolymer-Grafted Layers for Block Copolymer Self-Assembly
journal, May 2015

Controlling Domain Orientations in Thin Films of AB and ABA Block Copolymers
journal, August 2011

Perpendicular orientation of microdomains in PS-b-PMMA thin films on the PS brushed substrates
journal, January 2011

Engineering Silicon Oxide Surfaces Using Self-Assembled Monolayers
journal, October 2005

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

Controlled vapor deposition approach to generating substrate surface energy/chemistry gradients
journal, June 2011

Manipulating Nanoscale Morphologies in Cylinder-Forming Poly(styrene- b -isoprene- b -styrene) Thin Films Using Film Thickness and Substrate Surface Chemistry Gradients
journal, February 2013

Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates
journal, July 2003

Easy Orientation of Diblock Copolymers on Self-Assembled Monolayers Using UV Irradiation
journal, November 2009

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

Calculation of interfacial tension in polymer systems
journal, January 1971

Polar and Nonpolar Interactions in Adhesion
journal, January 1973

Surface and interfacial tensions of polymer melts. II. Poly(methyl methacrylate), poly(n-butyl methacrylate), and polystyrene
journal, February 1970

Forces involved in the adhesive process
journal, February 1970

Interfacial Segregation in Disordered Block Copolymers: Effect of Tunable Surface Potentials
journal, July 1997

Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions
journal, July 2009

Polymer surface modification by plasmas and photons
journal, May 1996

Interface and surface effects on the glass-transition temperature in thin polymer films
journal, January 1994

Dependence of the Glass Transition Temperature of Polymer Films on Interfacial Energy and Thickness
journal, July 2001

Extraordinary elevation of the glass transition temperature of thin polymer films grafted to silicon oxide substrates
journal, December 2001

Mechanisms of Ordering in Striped Patterns
journal, November 2000

Temperature Dependence of Order, Disorder, and Defects in Laterally Confined Diblock Copolymer Cylinder Monolayers
journal, July 2005

Observation of surface corrugation-induced alignment of lamellar microdomains in PS-b-PMMA thin films
journal, January 2009

Symmetric Diblock Copolymer Thin Films on Rough Substrates. Kinetics and Structure Formation in Pure Block Copolymer Thin Films
journal, March 2005

Processing Approaches for the Defect Engineering of Lamellar-Forming Block Copolymers in Thin Films
journal, December 2013

Probing surface and interface morphology with Grazing Incidence Small Angle X-Ray Scattering
journal, August 2009

Layering Transitions in Thin Films of Spherical-Domain Block Copolymers
journal, April 2007

Impact of Film Thickness on the Morphology of Mesoporous Carbon Films Using Organic−Organic Self-Assembly
journal, May 2011

Surface versus Confinement Induced Morphology Transition in Triblock Copolymer Films: A Grazing Incidence Small Angle Neutron Scattering Investigation
journal, October 2006

Impact of Out-of-Plane Translational Order in Block Copolymer Lithography
journal, December 2011

Directed Self-Assembly of Lamellar Copolymers: Effects of Interfacial Interactions on Domain Shape
journal, October 2012

Controlling interfacial interactions for directed self assembly of block copolymers
journal, May 2014

Rapid ordering of block copolymer thin films
journal, August 2016