Crystallization-Arrested Viscoelastic Phase Separation in Semiconducting Polymer Gels

Jing He; Xiaoqing Kong; Yuhao Wang; Michael Delaney; Dilhan M. Kalyon; Stephanie S. Lee

doi:10.1021/acsapm.8b00195

Crystallization-Arrested Viscoelastic Phase Separation in Semiconducting Polymer Gels

Jing He, Xiaoqing Kong, Yuhao Wang, Michael Delaney, Dilhan M. Kalyon, Stephanie S. Lee

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) in ortho-dichlorobenzene formed thermoreversible gels. Confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation (VPS), which arrested prematurely during the formation of micron-sized solvent-rich "holes"due to interchain crystallization. Cryogen-based scanning electron microscopy uncovered an interfibrillar network exhibiting nanosized pores. These networks formed to equal gel strengths when a third component, either small molecule phenyl-C61-butyric acid methyl ester or noncrystallizing regiorandom, poly(3-hexylthiophene), was added to the solution. Organic solar cells deposited with active layers from phase-separated solutions displayed 45% higher efficiency compared to reference cells. The demonstrated ability to arrest VPS enables control over the morphology of porous materials for applications ranging from membrane filtration to plastic foam manufacturing.

Original language	English (US)
Pages (from-to)	500-508
Number of pages	9
Journal	ACS Applied Polymer Materials
Volume	1
Issue number	3
DOIs	https://doi.org/10.1021/acsapm.8b00195
State	Published - Mar 8 2019

Keywords

confocal microscopy
cryo-SEM
gelation
organic photovoltaics
polymer crystallization
rheology
viscoelastic phase separation

ASJC Scopus subject areas

Polymers and Plastics
Process Chemistry and Technology
Organic Chemistry

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10.1021/acsapm.8b00195

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title = "Crystallization-Arrested Viscoelastic Phase Separation in Semiconducting Polymer Gels",

abstract = "Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) in ortho-dichlorobenzene formed thermoreversible gels. Confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation (VPS), which arrested prematurely during the formation of micron-sized solvent-rich {"}holes{"}due to interchain crystallization. Cryogen-based scanning electron microscopy uncovered an interfibrillar network exhibiting nanosized pores. These networks formed to equal gel strengths when a third component, either small molecule phenyl-C61-butyric acid methyl ester or noncrystallizing regiorandom, poly(3-hexylthiophene), was added to the solution. Organic solar cells deposited with active layers from phase-separated solutions displayed 45% higher efficiency compared to reference cells. The demonstrated ability to arrest VPS enables control over the morphology of porous materials for applications ranging from membrane filtration to plastic foam manufacturing.",

keywords = "confocal microscopy, cryo-SEM, gelation, organic photovoltaics, polymer crystallization, rheology, viscoelastic phase separation",

author = "Jing He and Xiaoqing Kong and Yuhao Wang and Michael Delaney and Kalyon, {Dilhan M.} and Lee, {Stephanie S.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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doi = "10.1021/acsapm.8b00195",

language = "English (US)",

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AU - He, Jing

AU - Kong, Xiaoqing

AU - Wang, Yuhao

AU - Delaney, Michael

AU - Kalyon, Dilhan M.

AU - Lee, Stephanie S.

PY - 2019/3/8

Y1 - 2019/3/8

N2 - Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) in ortho-dichlorobenzene formed thermoreversible gels. Confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation (VPS), which arrested prematurely during the formation of micron-sized solvent-rich "holes"due to interchain crystallization. Cryogen-based scanning electron microscopy uncovered an interfibrillar network exhibiting nanosized pores. These networks formed to equal gel strengths when a third component, either small molecule phenyl-C61-butyric acid methyl ester or noncrystallizing regiorandom, poly(3-hexylthiophene), was added to the solution. Organic solar cells deposited with active layers from phase-separated solutions displayed 45% higher efficiency compared to reference cells. The demonstrated ability to arrest VPS enables control over the morphology of porous materials for applications ranging from membrane filtration to plastic foam manufacturing.

AB - Through a combination of rheological characterization and temperature-variable imaging methods, a novel gelation pathway in dilute solutions of a semiconducting polymer to achieve interconnected, crystalline networks with hierarchical porosity is reported. Upon rapid cooling, solutions of regioregular poly(3-hexylthiophene) in ortho-dichlorobenzene formed thermoreversible gels. Confocal microscopy revealed cooling-induced structural rearrangement to progress through viscoelastic phase separation (VPS), which arrested prematurely during the formation of micron-sized solvent-rich "holes"due to interchain crystallization. Cryogen-based scanning electron microscopy uncovered an interfibrillar network exhibiting nanosized pores. These networks formed to equal gel strengths when a third component, either small molecule phenyl-C61-butyric acid methyl ester or noncrystallizing regiorandom, poly(3-hexylthiophene), was added to the solution. Organic solar cells deposited with active layers from phase-separated solutions displayed 45% higher efficiency compared to reference cells. The demonstrated ability to arrest VPS enables control over the morphology of porous materials for applications ranging from membrane filtration to plastic foam manufacturing.

KW - confocal microscopy

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KW - organic photovoltaics

KW - polymer crystallization

KW - rheology

KW - viscoelastic phase separation

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Crystallization-Arrested Viscoelastic Phase Separation in Semiconducting Polymer Gels

Abstract

Keywords

ASJC Scopus subject areas

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