Control of polymer-packing orientation in thin films through synthetic tailoring of backbone coplanarity

Mark S. Chen; Jeremy R. Niskala; David A. Unruh; Crystal K. Chu; Olivia P. Lee; Jean Frechet

doi:10.1021/cm402489a

Control of polymer-packing orientation in thin films through synthetic tailoring of backbone coplanarity

Mark S. Chen, Jeremy R. Niskala, David A. Unruh, Crystal K. Chu, Olivia P. Lee, Jean Frechet

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

210 Scopus citations

Abstract

Controlling solid-state order of π-conjugated polymers through macromolecular design is essential for achieving high electronic device performance; yet, it remains a challenge, especially with respect to polymer-packing orientation. Our work investigates the influence of backbone coplanarity on a polymer's preference to pack face-on or edge-on relative to the substrate. Isoindigo-based polymers were synthesized with increasing planarity by systematically substituting thiophenes for phenyl rings in the acceptor comonomer. This increasing backbone coplanarity, supported by density functional theory (DFT) calculations of representative trimers, leads to the narrowing of polymer band gaps as characterized by ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and cyclic voltammetry. Among the polymers studied, regiosymmetric II and TII polymers exhibited the highest hole mobilities in organic field-effect transistors (OFETs), while in organic photovoltaics (OPVs), TBII polymers that display intermediate levels of planarity provided the highest power conversion efficiencies. Upon thin-film analysis by atomic force microscropy (AFM) and grazing-incidence X-ray diffraction (GIXD), we discovered that polymer-packing orientation could be controlled by tuning polymer planarity and solubility. Highly soluble, planar polymers favor face-on orientation in thin films while the less soluble, nonplanar polymers favor an edge-on orientation. This study advances our fundamental understanding of how polymer structure influences nanostructural order and reveals a new synthetic strategy for the design of semiconducting materials with rationally engineered solid-state properties. © 2013 American Chemical Society.

Original language	English (US)
Pages (from-to)	4088-4096
Number of pages	9
Journal	Chemistry of Materials
Volume	25
Issue number	20
DOIs	https://doi.org/10.1021/cm402489a
State	Published - Oct 8 2013

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUS-C1-015-21
Acknowledgements: This work was supported in part by King Abdullah University of Science and Technology (KAUST) through the Center for Advanced Molecular Photovoltaics (CAMP) under Award No. KUS-C1-015-21, and the Frechet "various gifts" fund for the support of research in new materials. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource user facility, operated on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. M.S.C. thanks the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry for a fellowship; the assistance of Jessica C. Moreton is acknowledged with thanks.

ASJC Scopus subject areas

Materials Chemistry
General Chemical Engineering
General Chemistry

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title = "Control of polymer-packing orientation in thin films through synthetic tailoring of backbone coplanarity",

abstract = "Controlling solid-state order of π-conjugated polymers through macromolecular design is essential for achieving high electronic device performance; yet, it remains a challenge, especially with respect to polymer-packing orientation. Our work investigates the influence of backbone coplanarity on a polymer's preference to pack face-on or edge-on relative to the substrate. Isoindigo-based polymers were synthesized with increasing planarity by systematically substituting thiophenes for phenyl rings in the acceptor comonomer. This increasing backbone coplanarity, supported by density functional theory (DFT) calculations of representative trimers, leads to the narrowing of polymer band gaps as characterized by ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and cyclic voltammetry. Among the polymers studied, regiosymmetric II and TII polymers exhibited the highest hole mobilities in organic field-effect transistors (OFETs), while in organic photovoltaics (OPVs), TBII polymers that display intermediate levels of planarity provided the highest power conversion efficiencies. Upon thin-film analysis by atomic force microscropy (AFM) and grazing-incidence X-ray diffraction (GIXD), we discovered that polymer-packing orientation could be controlled by tuning polymer planarity and solubility. Highly soluble, planar polymers favor face-on orientation in thin films while the less soluble, nonplanar polymers favor an edge-on orientation. This study advances our fundamental understanding of how polymer structure influences nanostructural order and reveals a new synthetic strategy for the design of semiconducting materials with rationally engineered solid-state properties. {\textcopyright} 2013 American Chemical Society.",

author = "Chen, {Mark S.} and Niskala, {Jeremy R.} and Unruh, {David A.} and Chu, {Crystal K.} and Lee, {Olivia P.} and Jean Frechet",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: This work was supported in part by King Abdullah University of Science and Technology (KAUST) through the Center for Advanced Molecular Photovoltaics (CAMP) under Award No. KUS-C1-015-21, and the Frechet {"}various gifts{"} fund for the support of research in new materials. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource user facility, operated on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. M.S.C. thanks the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry for a fellowship; the assistance of Jessica C. Moreton is acknowledged with thanks.",

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AU - Niskala, Jeremy R.

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AU - Chu, Crystal K.

AU - Lee, Olivia P.

AU - Frechet, Jean

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledged KAUST grant number(s): KUS-C1-015-21 Acknowledgements: This work was supported in part by King Abdullah University of Science and Technology (KAUST) through the Center for Advanced Molecular Photovoltaics (CAMP) under Award No. KUS-C1-015-21, and the Frechet "various gifts" fund for the support of research in new materials. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource user facility, operated on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences. M.S.C. thanks the Camille and Henry Dreyfus Postdoctoral Program in Environmental Chemistry for a fellowship; the assistance of Jessica C. Moreton is acknowledged with thanks.

PY - 2013/10/8

Y1 - 2013/10/8

N2 - Controlling solid-state order of π-conjugated polymers through macromolecular design is essential for achieving high electronic device performance; yet, it remains a challenge, especially with respect to polymer-packing orientation. Our work investigates the influence of backbone coplanarity on a polymer's preference to pack face-on or edge-on relative to the substrate. Isoindigo-based polymers were synthesized with increasing planarity by systematically substituting thiophenes for phenyl rings in the acceptor comonomer. This increasing backbone coplanarity, supported by density functional theory (DFT) calculations of representative trimers, leads to the narrowing of polymer band gaps as characterized by ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and cyclic voltammetry. Among the polymers studied, regiosymmetric II and TII polymers exhibited the highest hole mobilities in organic field-effect transistors (OFETs), while in organic photovoltaics (OPVs), TBII polymers that display intermediate levels of planarity provided the highest power conversion efficiencies. Upon thin-film analysis by atomic force microscropy (AFM) and grazing-incidence X-ray diffraction (GIXD), we discovered that polymer-packing orientation could be controlled by tuning polymer planarity and solubility. Highly soluble, planar polymers favor face-on orientation in thin films while the less soluble, nonplanar polymers favor an edge-on orientation. This study advances our fundamental understanding of how polymer structure influences nanostructural order and reveals a new synthetic strategy for the design of semiconducting materials with rationally engineered solid-state properties. © 2013 American Chemical Society.

AB - Controlling solid-state order of π-conjugated polymers through macromolecular design is essential for achieving high electronic device performance; yet, it remains a challenge, especially with respect to polymer-packing orientation. Our work investigates the influence of backbone coplanarity on a polymer's preference to pack face-on or edge-on relative to the substrate. Isoindigo-based polymers were synthesized with increasing planarity by systematically substituting thiophenes for phenyl rings in the acceptor comonomer. This increasing backbone coplanarity, supported by density functional theory (DFT) calculations of representative trimers, leads to the narrowing of polymer band gaps as characterized by ultraviolet-visible-near infrared (UV-vis-NIR) spectroscopy and cyclic voltammetry. Among the polymers studied, regiosymmetric II and TII polymers exhibited the highest hole mobilities in organic field-effect transistors (OFETs), while in organic photovoltaics (OPVs), TBII polymers that display intermediate levels of planarity provided the highest power conversion efficiencies. Upon thin-film analysis by atomic force microscropy (AFM) and grazing-incidence X-ray diffraction (GIXD), we discovered that polymer-packing orientation could be controlled by tuning polymer planarity and solubility. Highly soluble, planar polymers favor face-on orientation in thin films while the less soluble, nonplanar polymers favor an edge-on orientation. This study advances our fundamental understanding of how polymer structure influences nanostructural order and reveals a new synthetic strategy for the design of semiconducting materials with rationally engineered solid-state properties. © 2013 American Chemical Society.

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JF - Chemistry of Materials

IS - 20

ER -

Control of polymer-packing orientation in thin films through synthetic tailoring of backbone coplanarity

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