High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments

Angelopoulou, Polyxeni P.; Kearney, Logan T.; Keum, Jong Kahk; Collins, Liam; Kumar, Rajeev; Sakellariou, Georgios; Advincula, Rigoberto C.; Mays, Jimmy W.; Hong, Kunlun

doi:10.1039/d3ta01386c

Title: High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments

Abstract

Block copolymers exhibiting an enhanced segregation strength due to an underlying high Flory–Huggins interaction parameter (high χ) have attracted considerable attention because of their potential of forming microphase-separated domains with very small feature sizes (<10 nm) useful for next-generation lithography. Here, we report the synthesis, characterization, and self-assembly of poly(styrene)-block-poly(2-vinylpyridine N-oxide) (PS-b-P2VPNO) and poly(styrene)-block-poly(4-vinylpyridine N-oxide) (PS-b-P4VPNO) block copolymers. These PS-b-PVPNOs were obtained from the oxidation of their precursors, poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) and poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), respectively. The PS-b-PVPNOs exhibit an enhanced segregation as revealed by ordered cylindrical and lamellar structures in the sub-10 nm scale from copolymers with relatively low molecular weight. The morphologies and periodicities of the ordered structures were determined by small-angle X-ray scattering, while atomic-force microscopy was used to image the self-assembly in thin films. Estimates of the changes in disorder–order transition temperature and domain spacing are derived from a theory based on the effects of dipolar interactions. All the experimentally observed morphological changes resulting from the oxidation of P2VP and P4VP precursors can be qualitatively explained in terms of an increased dipole moment of vinylpyridine N-oxide segments. Therefore, our results demonstrate that PVPNO based block copolymers are versatile candidates toward nanopatterned structures with small feature sizes critical formore »« less

Authors:

Angelopoulou, Polyxeni P. ^[1]; Kearney, Logan T. ^[2];

^[2];

^[3]; Advincula, Rigoberto C. ^[2];

^[4];

^[2]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); National and Kapodistrian University of Athens (Greece)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
National and Kapodistrian University of Athens (Greece)
University of Tennessee, Knoxville, TN (United States)

Publication Date:: Thu Apr 20 00:00:00 EDT 2023

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1986223

Alternate Identifier(s):: OSTI ID: 1971381

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Volume: 11; Journal Issue: 18; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Angelopoulou, Polyxeni P., Kearney, Logan T., Keum, Jong Kahk, Collins, Liam, Kumar, Rajeev, Sakellariou, Georgios, Advincula, Rigoberto C., Mays, Jimmy W., and Hong, Kunlun. High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments.  United States: N. p., 2023. 
Web.  doi:10.1039/d3ta01386c.

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                    Angelopoulou, Polyxeni P., Kearney, Logan T., Keum, Jong Kahk, Collins, Liam, Kumar, Rajeev, Sakellariou, Georgios, Advincula, Rigoberto C., Mays, Jimmy W., & Hong, Kunlun. High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments.  United States.  https://doi.org/10.1039/d3ta01386c

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                    Angelopoulou, Polyxeni P., Kearney, Logan T., Keum, Jong Kahk, Collins, Liam, Kumar, Rajeev, Sakellariou, Georgios, Advincula, Rigoberto C., Mays, Jimmy W., and Hong, Kunlun. Thu .  
"High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments".  United States.  https://doi.org/10.1039/d3ta01386c.  https://www.osti.gov/servlets/purl/1986223.

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@article{osti_1986223,

  title        = {High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments},

  author       = {Angelopoulou, Polyxeni P. and Kearney, Logan T. and Keum, Jong Kahk and Collins, Liam and Kumar, Rajeev and Sakellariou, Georgios and Advincula, Rigoberto C. and Mays, Jimmy W. and Hong, Kunlun},

  abstractNote = {Block copolymers exhibiting an enhanced segregation strength due to an underlying high Flory–Huggins interaction parameter (high χ) have attracted considerable attention because of their potential of forming microphase-separated domains with very small feature sizes (<10 nm) useful for next-generation lithography. Here, we report the synthesis, characterization, and self-assembly of poly(styrene)-block-poly(2-vinylpyridine N-oxide) (PS-b-P2VPNO) and poly(styrene)-block-poly(4-vinylpyridine N-oxide) (PS-b-P4VPNO) block copolymers. These PS-b-PVPNOs were obtained from the oxidation of their precursors, poly(styrene)-block-poly(2-vinylpyridine) (PS-b-P2VP) and poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), respectively. The PS-b-PVPNOs exhibit an enhanced segregation as revealed by ordered cylindrical and lamellar structures in the sub-10 nm scale from copolymers with relatively low molecular weight. The morphologies and periodicities of the ordered structures were determined by small-angle X-ray scattering, while atomic-force microscopy was used to image the self-assembly in thin films. Estimates of the changes in disorder–order transition temperature and domain spacing are derived from a theory based on the effects of dipolar interactions. All the experimentally observed morphological changes resulting from the oxidation of P2VP and P4VP precursors can be qualitatively explained in terms of an increased dipole moment of vinylpyridine N-oxide segments. Therefore, our results demonstrate that PVPNO based block copolymers are versatile candidates toward nanopatterned structures with small feature sizes critical for the future microelectronics industry and beyond.},

  doi          = {10.1039/d3ta01386c},

  journal      = {Journal of Materials Chemistry. A},

  number       = 18,

  volume       = 11,

  place        = {United States},

  year         = {Thu Apr 20 00:00:00 EDT 2023},

  month        = {Thu Apr 20 00:00:00 EDT 2023}

}

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Amphiphilic block copolymers: Micellization and solubilization

Conference Foerster, S ; Wenz, E ; Zisenis, M

Amphiphilic block copolymers exhibit self-assembly properties of low molecular weight surfactants together with the superior material properties of polymers. We investigated the formation of polymeric micelles of a series of Poly(styrene-b-4-vinylpyridine) (PS-P4VP) block copolymers in selective solvents for PS (toluene, THF). The aggregation number exhibits a strong dependence on the degree of polymerization of the core-forming P4VP block, characteristic for micellization in the strong segregation regime. The polarity of the P4VP-block can be further increased by quaternization, N-oxidation, or sulfobetain formation. These micelles readily solubilize inorganic salts like CuCl and Cd(ClO{sub 4}){sub 2}. The latter reacts easily with H{sub 2}Smore »« less
Symmetry Transition in Thin Films of Diblock Copolymer/Homopolymer Blends

Journal Article Mishra, Vindhya ; Hur, Su-mi ; Cochran, Eric W ; ... - Macromolecules

The effect of blending small weight fractions of low molecular weight majority block homopolymer on the structure of multilayer films of spherical morphology poly(styrene-b-2vinylpyridine) [PS-P2VP] has been studied. The structure of the films was characterized with grazing-incidence small-angle X-ray scattering (GISAXS) and transmission electron microscopy (TEM). In multilayer films of PS-P2VP, competition between hexagonal packing of the spherical domains preferred at the surfaces with the BCC (110) packing preferred by the internal layers leads to a transition in the packing symmetry as the number of sphere layers (n) is increased.(1) Neat PS-P2VP exhibits hexagonal close-packed (HCP) symmetry up through nmore »« less
https://doi.org/10.1021/ma901891b

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Title: High-χ diblock copolymers containing poly(vinylpyridine-N-oxide) segments

Abstract

Citation Formats

Reduction of (Meth)acrylate-Based Block Copolymers Provides Access to Self-Assembled Materials with Ultrasmall Domains journal, August 2018

Origin of the Difference in Order−Disorder Transition Temperature between Polystyrene- block -poly(2-vinylpyridine) and Polystyrene- block -poly(4-vinylpyridine) Copolymers journal, March 2007

Phase Behavior of Deuterated Polystyrene- b lock -poly( n -pentyl methacrylate) Copolymers journal, April 2003

Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains journal, April 2018

Poly(vinylpyridine) Segments in Block Copolymers: Synthesis, Self-Assembly, and Versatility journal, February 2019

Mode of Action of Poly(vinylpyridine-N-oxide) in Preventing Silicosis: Effective Scavenging of Carbonate Anion Radical journal, December 2005

Thermodynamic Association Behaviors of Sodium Dodecyl Sulfate (SDS) with Poly(4-vinylpyridine N-oxide) (PVPNO) at Different pH Values and Ionic Strengths journal, March 2017

Design of high-χ block copolymers for lithography journal, August 2014

Poly(alkylvinylpyridine 1-oxides) and corresponding alkylpyridine oxides: electronic spectra and interaction with silicic acid journal, January 1969

Heterocyclic N-Oxides and N-Imides journal, January 1992

Poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers: synthesis, self-assembly and interaction journal, January 2015

Viscosity and light scattering studies of poly(4-vinylpyridine N-oxide) in solution journal, January 1996

Theory of Microphase Separation in Block Copolymers journal, November 1980

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

Gallol-Based Block Copolymer with a High Flory–Huggins Interaction Parameter for Next-Generation Lithography journal, December 2022

Realizing 5.4 nm Full Pitch Lamellar Microdomains by a Solid-State Transformation journal, September 2017

Evaluation of segmental interaction by small-angle x-ray scattering based on the random-phase approximation for asymmetric, polydisperse triblock copolymers journal, May 1992

Measurements of the Flory−Huggins Interaction Parameter for Polystyrene−Poly(4-vinylpyridine) Blends journal, July 1997

Heterotelechelic homopolymers mimicking high χ – ultralow N block copolymers with sub-2 nm domain size journal, January 2022

Current status and future directions of self-assembled block copolymer membranes for molecular separations journal, January 2021

Well-Organized Dense Arrays of Nanodomains in Thin Films of Poly(dimethylsiloxane)- b -poly(lactide) Diblock Copolymers journal, October 2013

Synthese von14C-markiertem Polyvinylpyridin-N-oxid journal, October 1968

Accurate diblock copolymer phase boundaries at strong segregations journal, December 1996

Block Copolymer Thermodynamics: Theory and Experiment journal, October 1990

Self-Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications journal, February 2009

The Diversity of Heterocyclic N-oxide Molecules: Highlights on their Potential in Organic Synthesis, Catalysis and Drug Applications journal, July 2019

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

Designing high χ copolymer materials for nanotechnology applications: A systematic bulk vs. thin films approach journal, December 2022

Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry journal, August 2019

Design and Morphological Investigation of High-χ Catechol-Containing Styrenic Block Copolymers journal, July 2022

Block Copolymer with an Extremely High Block-to-Block Interaction for a Significant Reduction of Line-Edge Fluctuations in Self-Assembled Patterns journal, August 2016

Poly(vinyl pyridine) and Its Quaternized Derivatives: Understanding Their Solvation and Solid State Properties journal, February 2022

Self-assembly of block copolymers towards mesoporous materials for energy storage and conversion systems journal, January 2020

Poly(vinyl pyridine)s: Simple reactive polymers with multiple applications journal, December 1984

Thin Film Self-Assembly of Poly(trimethylsilylstyrene- b - d , l -lactide) with Sub-10 nm Domains journal, October 2012

Block Copolymers: Synthesis, Self-Assembly, and Applications journal, October 2017

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

Polyanionic pH-responsive polystyrene-b-poly(4-vinyl pyridine-N-oxide) isoporous membranes journal, March 2016

Poly(vinylpyridine N-oxide) supported dichromates as new effective, mild and versatile oxidizing reagents for various organic compounds journal, September 1992

Anionic polymerization: High vacuum techniques journal, January 2000

A Reactive Platform Approach for the Rapid Synthesis and Discovery of High χ/Low N Block Polymers journal, September 2016

Synthesis and morphological characterization of linear and miktoarm star poly(solketal methacrylate)-block-polystyrene copolymers journal, May 2023

Cross-linked poly(4-vinylpyridine-N-oxide) as a polymer-supported oxygen atom transfer reagent journal, October 2019

RECENT JAPANESE WORK ON THE CHEMISTRY OF PYRIDINE 1-OXIDE AND RELATED COMPOUNDS1 journal, May 1953

Fabrication of Sub-3 nm Feature Size Based on Block Copolymer Self-Assembly for Next-Generation Nanolithography journal, August 2017

Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts journal, August 2019

The interaction of poly-2-vinylpyridine 1-oxide and poly-4-vinylpyridine 1-oxide with monosilicic acid journal, January 1968

Block copolymer strategies for solar cell technology journal, June 2011

Polylactide−Poly(dimethylsiloxane)−Polylactide Triblock Copolymers as Multifunctional Materials for Nanolithographic Applications journal, January 2010

Self-Assembly of an Ultrahigh-χ Block Copolymer with Versatile Etch Selectivity journal, August 2018

Pyridine-N-Oxide journal, April 1955

Heat capacity and index of refraction of polyzwitterions journal, September 2022

Interaction of some Polyvinylpyridine Oxides with Polysilicic Acid and its relationship to their Ability to inhibit Silica Fibrosis journal, November 1967

Experimental techniques in high-vacuum anionic polymerization journal, January 2005

Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography journal, February 2014

Enabling future nanomanufacturing through block copolymer self-assembly: A review journal, December 2020

Fabrication of High χ-Low N Block Copolymers with Thermally Stable Sub-5 nm Microdomains Using Polyzwitterion as a Constituent Block journal, October 2021

Evaluation of χ Parameter book, January 2015

Solution Self-Assembly of Chalcogen-Bonding Polymer Partners journal, July 2020

Heteroaromatic N-Oxides in Asymmetric Catalysis: A Review journal, January 2020

Poly(styrene-b-2-vinylpyridine-1-oxide) and poly(dimethylsiloxane-b-2 vinylpyridine-1-oxide) diblock copolymers. 1. Preparation and characterisation journal, May 1992

Sub-3-Nanometer Domain Spacings of Ultrahigh-χ Multiblock Copolymers with Pendant Ionic Groups journal, October 2021

Poly(vinylpyridine)-containing block copolymers for smart, multicompartment particles journal, January 2022

Über Pyridin‐, Chinolin‐ und Isochinolin‐ N ‐oxyd journal, September 1926

Sustainable Chemistry Method to Improve the Wash-off Process of Reactive Dyes on Cotton journal, March 2015

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

Characterization of poly(4‐vinylpyridine 1‐oxide) by free‐solution capillary electrophoresis and micellar electrokinetic chromatography journal, July 2008

Reduction of (Meth)acrylate-Based Block Copolymers Provides Access to Self-Assembled Materials with Ultrasmall Domains
journal, August 2018

Origin of the Difference in Order−Disorder Transition Temperature between Polystyrene- block -poly(2-vinylpyridine) and Polystyrene- block -poly(4-vinylpyridine) Copolymers
journal, March 2007

Phase Behavior of Deuterated Polystyrene- b lock -poly( n -pentyl methacrylate) Copolymers
journal, April 2003

Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains
journal, April 2018

Poly(vinylpyridine) Segments in Block Copolymers: Synthesis, Self-Assembly, and Versatility
journal, February 2019

Mode of Action of Poly(vinylpyridine-N-oxide) in Preventing Silicosis: Effective Scavenging of Carbonate Anion Radical
journal, December 2005

Thermodynamic Association Behaviors of Sodium Dodecyl Sulfate (SDS) with Poly(4-vinylpyridine N-oxide) (PVPNO) at Different pH Values and Ionic Strengths
journal, March 2017

Design of high-χ block copolymers for lithography
journal, August 2014

Poly(alkylvinylpyridine 1-oxides) and corresponding alkylpyridine oxides: electronic spectra and interaction with silicic acid
journal, January 1969

Heterocyclic N-Oxides and N-Imides
journal, January 1992

Poly(4-vinylpyridine)-block-poly(N-acryloylpiperidine) diblock copolymers: synthesis, self-assembly and interaction
journal, January 2015

Viscosity and light scattering studies of poly(4-vinylpyridine N-oxide) in solution
journal, January 1996

Theory of Microphase Separation in Block Copolymers
journal, November 1980

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

Gallol-Based Block Copolymer with a High Flory–Huggins Interaction Parameter for Next-Generation Lithography
journal, December 2022

Realizing 5.4 nm Full Pitch Lamellar Microdomains by a Solid-State Transformation
journal, September 2017

Evaluation of segmental interaction by small-angle x-ray scattering based on the random-phase approximation for asymmetric, polydisperse triblock copolymers
journal, May 1992

Measurements of the Flory−Huggins Interaction Parameter for Polystyrene−Poly(4-vinylpyridine) Blends
journal, July 1997

Heterotelechelic homopolymers mimicking high χ – ultralow N block copolymers with sub-2 nm domain size
journal, January 2022

Current status and future directions of self-assembled block copolymer membranes for molecular separations
journal, January 2021

Well-Organized Dense Arrays of Nanodomains in Thin Films of Poly(dimethylsiloxane)- b -poly(lactide) Diblock Copolymers
journal, October 2013

Synthese von14C-markiertem Polyvinylpyridin-N-oxid
journal, October 1968

Accurate diblock copolymer phase boundaries at strong segregations
journal, December 1996

Block Copolymer Thermodynamics: Theory and Experiment
journal, October 1990

Self-Assembled Block Copolymer Aggregates: From Micelles to Vesicles and their Biological Applications
journal, February 2009

The Diversity of Heterocyclic N-oxide Molecules: Highlights on their Potential in Organic Synthesis, Catalysis and Drug Applications
journal, July 2019

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

Designing high χ copolymer materials for nanotechnology applications: A systematic bulk vs. thin films approach
journal, December 2022

Recent advances in thermoplastic elastomers from living polymerizations: Macromolecular architectures and supramolecular chemistry
journal, August 2019

Design and Morphological Investigation of High-χ Catechol-Containing Styrenic Block Copolymers
journal, July 2022

Block Copolymer with an Extremely High Block-to-Block Interaction for a Significant Reduction of Line-Edge Fluctuations in Self-Assembled Patterns
journal, August 2016

Poly(vinyl pyridine) and Its Quaternized Derivatives: Understanding Their Solvation and Solid State Properties
journal, February 2022

Self-assembly of block copolymers towards mesoporous materials for energy storage and conversion systems
journal, January 2020

Poly(vinyl pyridine)s: Simple reactive polymers with multiple applications
journal, December 1984

Thin Film Self-Assembly of Poly(trimethylsilylstyrene- b - d , l -lactide) with Sub-10 nm Domains
journal, October 2012

Block Copolymers: Synthesis, Self-Assembly, and Applications
journal, October 2017

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

Polyanionic pH-responsive polystyrene-b-poly(4-vinyl pyridine-N-oxide) isoporous membranes
journal, March 2016

Poly(vinylpyridine N-oxide) supported dichromates as new effective, mild and versatile oxidizing reagents for various organic compounds
journal, September 1992

Anionic polymerization: High vacuum techniques
journal, January 2000

A Reactive Platform Approach for the Rapid Synthesis and Discovery of High χ/Low N Block Polymers
journal, September 2016

Synthesis and morphological characterization of linear and miktoarm star poly(solketal methacrylate)-block-polystyrene copolymers
journal, May 2023

Cross-linked poly(4-vinylpyridine-N-oxide) as a polymer-supported oxygen atom transfer reagent
journal, October 2019

RECENT JAPANESE WORK ON THE CHEMISTRY OF PYRIDINE 1-OXIDE AND RELATED COMPOUNDS¹
journal, May 1953

Fabrication of Sub-3 nm Feature Size Based on Block Copolymer Self-Assembly for Next-Generation Nanolithography
journal, August 2017

Understanding the effects of dipolar interactions on the thermodynamics of diblock copolymer melts
journal, August 2019

The interaction of poly-2-vinylpyridine 1-oxide and poly-4-vinylpyridine 1-oxide with monosilicic acid
journal, January 1968

Block copolymer strategies for solar cell technology
journal, June 2011

Polylactide−Poly(dimethylsiloxane)−Polylactide Triblock Copolymers as Multifunctional Materials for Nanolithographic Applications
journal, January 2010

Self-Assembly of an Ultrahigh-χ Block Copolymer with Versatile Etch Selectivity
journal, August 2018

Pyridine-N-Oxide
journal, April 1955

Heat capacity and index of refraction of polyzwitterions
journal, September 2022

Interaction of some Polyvinylpyridine Oxides with Polysilicic Acid and its relationship to their Ability to inhibit Silica Fibrosis
journal, November 1967

Experimental techniques in high-vacuum anionic polymerization
journal, January 2005

Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)- block -poly(methyl methacrylate) Block Polymers for Lithography
journal, February 2014

Enabling future nanomanufacturing through block copolymer self-assembly: A review
journal, December 2020

Fabrication of High χ-Low N Block Copolymers with Thermally Stable Sub-5 nm Microdomains Using Polyzwitterion as a Constituent Block
journal, October 2021

Evaluation of χ Parameter
book, January 2015

Solution Self-Assembly of Chalcogen-Bonding Polymer Partners
journal, July 2020

Heteroaromatic N-Oxides in Asymmetric Catalysis: A Review
journal, January 2020

Poly(styrene-b-2-vinylpyridine-1-oxide) and poly(dimethylsiloxane-b-2 vinylpyridine-1-oxide) diblock copolymers. 1. Preparation and characterisation
journal, May 1992

Sub-3-Nanometer Domain Spacings of Ultrahigh-χ Multiblock Copolymers with Pendant Ionic Groups
journal, October 2021

Poly(vinylpyridine)-containing block copolymers for smart, multicompartment particles
journal, January 2022

Über Pyridin‐, Chinolin‐ und Isochinolin‐ N ‐oxyd
journal, September 1926

Sustainable Chemistry Method to Improve the Wash-off Process of Reactive Dyes on Cotton
journal, March 2015

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

Characterization of poly(4‐vinylpyridine 1‐oxide) by free‐solution capillary electrophoresis and micellar electrokinetic chromatography
journal, July 2008