Side chain length affects backbone dynamics in poly(3-alkylthiophene)s

Zhan, Pengfei; Zhang, Wenlin; Jacobs, Ian E.; Nisson, David M.; Xie, Renxuan; Weissen, Albree R.; Colby, Ralph H.; Moulé, Adam J.; Milner, Scott T.; Maranas, Janna K.; Gomez, Enrique D.

doi:10.1002/polb.24637

Title: Side chain length affects backbone dynamics in poly(3-alkylthiophene)s

Abstract

Charge transport in conjugated polymers may be governed not only by the static microstructure but also fluctuations of backbone segments. Using molecular dynamics simulations, we predict the role of side chains in the backbone dynamics for regiorandom poly(3-alkylthiophene-2,5-diyl)s (P3ATs). Here, we show that the backbone of poly(3-dodecylthiophene-2-5-diyl) (P3DDT) moves faster than that of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a result of the faster motion of the longer side chains. To verify our predictions, we investigated the structures and dynamics of regiorandom P3ATs with neutron scattering and solid state NMR. Measurements of spin-lattice relaxations (T1) using NMR support our prediction of faster motion for side chain atoms that are farther away from the backbone. Using small-angle neutron scattering (SANS), we confirmed that regiorandom P3ATs are amorphous at about 300K, although microphase separation between the side chains and backbones is apparent. Furthermore, Quasi-elastic neutron scattering (QENS) reveals that thiophene backbone motion is enhanced as the side chain length increases from hexyl to dodecyl. The faster motion of longer side chains leads to faster backbone dynamics, which in turn may affect charge transport for conjugated polymers.

Authors:

Zhan, Pengfei ^[1]; Zhang, Wenlin ^[1]; Jacobs, Ian E. ^[2]; Nisson, David M. ^[2]; Xie, Renxuan ^[1]; Weissen, Albree R. ^[1]; Colby, Ralph H. ^[1]; Moulé, Adam J. ^[3]; Milner, Scott T. ^[1]; Maranas, Janna K. ^[1];

^[4]

Pennsylvania State Univ., University Park, PA (United States)
Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Pennsylvania State Univ., University Park, PA (United States)
Pennsylvania State Univ., University Park, PA (United States). Materials Research Inst.

Publication Date:: Mon Aug 27 00:00:00 EDT 2018

Research Org.:: Univ. of California, Davis, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1537607

Alternate Identifier(s):: OSTI ID: 1467533

Grant/Contract Number:: SC0010419; DMR‐1629006

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Polymer Science. Part B, Polymer Physics

Additional Journal Information:: Journal Volume: 56; Journal Issue: 17; Journal ID: ISSN 0887-6266

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; Polymer Science; Conjugated Polymers; Charge Transport; Side chain motion; Quasi Elastic Neutron Scattering; solid state NMR

Citation Formats


                    Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., and Gomez, Enrique D. Side chain length affects backbone dynamics in poly(3-alkylthiophene)s.  United States: N. p., 2018. 
Web.  doi:10.1002/polb.24637.

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                    Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., & Gomez, Enrique D. Side chain length affects backbone dynamics in poly(3-alkylthiophene)s.  United States.  https://doi.org/10.1002/polb.24637

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                    Zhan, Pengfei, Zhang, Wenlin, Jacobs, Ian E., Nisson, David M., Xie, Renxuan, Weissen, Albree R., Colby, Ralph H., Moulé, Adam J., Milner, Scott T., Maranas, Janna K., and Gomez, Enrique D. Mon .  
"Side chain length affects backbone dynamics in poly(3-alkylthiophene)s".  United States.  https://doi.org/10.1002/polb.24637.  https://www.osti.gov/servlets/purl/1537607.

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@article{osti_1537607,

  title        = {Side chain length affects backbone dynamics in poly(3-alkylthiophene)s},

  author       = {Zhan, Pengfei and Zhang, Wenlin and Jacobs, Ian E. and Nisson, David M. and Xie, Renxuan and Weissen, Albree R. and Colby, Ralph H. and Moulé, Adam J. and Milner, Scott T. and Maranas, Janna K. and Gomez, Enrique D.},

  abstractNote = {Charge transport in conjugated polymers may be governed not only by the static microstructure but also fluctuations of backbone segments. Using molecular dynamics simulations, we predict the role of side chains in the backbone dynamics for regiorandom poly(3-alkylthiophene-2,5-diyl)s (P3ATs). Here, we show that the backbone of poly(3-dodecylthiophene-2-5-diyl) (P3DDT) moves faster than that of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a result of the faster motion of the longer side chains. To verify our predictions, we investigated the structures and dynamics of regiorandom P3ATs with neutron scattering and solid state NMR. Measurements of spin-lattice relaxations (T1) using NMR support our prediction of faster motion for side chain atoms that are farther away from the backbone. Using small-angle neutron scattering (SANS), we confirmed that regiorandom P3ATs are amorphous at about 300K, although microphase separation between the side chains and backbones is apparent. Furthermore, Quasi-elastic neutron scattering (QENS) reveals that thiophene backbone motion is enhanced as the side chain length increases from hexyl to dodecyl. The faster motion of longer side chains leads to faster backbone dynamics, which in turn may affect charge transport for conjugated polymers.},

  doi          = {10.1002/polb.24637},

  journal      = {Journal of Polymer Science. Part B, Polymer Physics},

  number       = 17,

  volume       = 56,

  place        = {United States},

  year         = {Mon Aug 27 00:00:00 EDT 2018},

  month        = {Mon Aug 27 00:00:00 EDT 2018}

}

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Title: Side chain length affects backbone dynamics in poly(3-alkylthiophene)s

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Interplay of Surface Chemistry and Ion Content in Nanoparticle-Filled Solid Polymer Electrolytes journal, May 2014

Functionalized Acenes and Heteroacenes for Organic Electronics journal, December 2006

Alkyl-Chain-Length-Independent Hole Mobility via Morphological Control with Poly(3-alkylthiophene) Nanofibers journal, March 2010

Predicting Nematic Phases of Semiflexible Polymers journal, February 2015

Hydration dependent studies of highly aligned multilayer lipid membranes by neutron scattering journal, October 2010

A general relationship between disorder, aggregation and charge transport in conjugated polymers journal, August 2013

Molecular Dynamics of Regioregular Poly(3-hexylthiophene) Investigated by NMR Relaxation and an Interpretation of Temperature Dependent Optical Absorption journal, January 2010

Glass Transition Temperature of Conjugated Polymers by Oscillatory Shear Rheometry journal, June 2017

Temperature-Dependent Dynamics of Polyalkylthiophene Conjugated Polymers: A Combined Neutron Scattering and Simulation Study journal, November 2015

Charge Transport Physics of Conjugated Polymer Field-Effect Transistors journal, June 2010

The effect of environment on local dynamics of macromolecules journal, February 2007

Internal Dynamics in SDS Micelles: Neutron Scattering Study journal, December 2010

Indacenodithiophene Semiconducting Polymers for High-Performance, Air-Stable Transistors journal, August 2010

The extended Q -range small-angle neutron scattering diffractometer at the SNS journal, July 2010

Understanding the Microscopic Origin of the Very High Charge Mobility in PBTTT: Tolerance of Thermal Disorder journal, September 2013

Device Physics of Solution-Processed Organic Field-Effect Transistors journal, October 2005

Solvatochromism and Conformational Changes in Fully Dissolved Poly(3-alkylthiophene)s journal, December 2014

The path to ubiquitous and low-cost organic electronic appliances on plastic journal, April 2004

Predicting Chain Dimensions of Semiflexible Polymers from Dihedral Potentials journal, September 2014

Dynamics of PEO in Blends with PMMA: Study of the Effects of Blend Composition via Quasi-Elastic Neutron Scattering journal, May 2008

Liquid-crystalline semiconducting polymers with high charge-carrier mobility journal, March 2006

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data journal, November 2009

Effect of Side-Chain Length on the Polymer Chain Dynamics of Poly(alkyl methacrylate)s in Solution journal, December 2013

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids journal, January 1996

A Molecular View of Melting in Anhydrous Phospholipidic Membranes journal, January 2007

GROMACS: A message-passing parallel molecular dynamics implementation journal, September 1995

Charge Transport in Organic Semiconductors journal, April 2007

Dynamics of the α relaxation of a glass-forming polymeric system: Dielectric, mechanical, nuclear-magnetic-resonance, and neutron-scattering studies journal, October 1991

Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function journal, January 1970

High-Lamellar Ordering and Amorphous-Like π-Network in Short-Chain Thiazolothiazole−Thiophene Copolymers Lead to High Mobilities journal, February 2009

X-ray structural studies of poly(3-alkylthiophenes): an example of an inverse comb journal, August 1992

Observation of fragile-to-strong dynamic crossover in protein hydration water journal, June 2006

Effect of Blending with Poly(ethylene oxide) on the Dynamics of Poly(methyl methacrylate): A Quasi-Elastic Neutron Scattering Approach journal, December 2004

The high-flux backscattering spectrometer at the NIST Center for Neutron Research journal, May 2003

Interplay of Structure and Dynamics in Functional Macromolecular and Supramolecular Systems As Revealed by Magnetic Resonance Spectroscopy journal, August 2015

Challenges and Opportunities in the Development of Conjugated Block Copolymers for Photovoltaics journal, September 2015

Well-defined, high molecular weight poly(3-alkylthiophene)s in thin-film transistors: side chain invariance in field-effect mobility journal, January 2010

Alkyl chain length dependence of the field-effect carrier mobility in regioregular poly(3-alkylthiophene)s journal, January 2005

Coarse-grained simulations of the solution-phase self-assembly of poly(3-hexylthiophene) nanostructures journal, January 2013

Conductivity relaxation and chain motions in conjugated conducting polymers: neutral poly(3-alkylthiophenes) journal, May 1993

Influence of side-chain length on main- and side-chain dynamics in poly-n-acrylates: A solid-state NMR study journal, September 2004

Relaxation Effects in Nuclear Magnetic Resonance Absorption journal, April 1948

Polymer Chain Shape of Poly(3-alkylthiophenes) in Solution Using Small-Angle Neutron Scattering journal, February 2013

Coarse-Grained Computer Simulations of Polymer/Fullerene Bulk Heterojunctions for Organic Photovoltaic Applications journal, December 2009

Effect of side chain length on molecular ordering and field-effect mobility in poly(3-alkylthiophene) transistors journal, December 2006

Ultrathin Body Poly(3-hexylthiophene) Transistors with Improved Short-Channel Performance journal, February 2013

The measurement of proton-enhanced carbon-13 T1 values by a method which suppresses artifacts journal, June 1978

Water mobility in a water-soaked nafion® membrane: A high-resolution neutron quasielastic study journal, March 1982

Functionalized Acenes and Heteroacenes for Organic Electronics journal, May 2007

Charge Transport in Organic Semiconductors journal, July 2007

Relaxation Effects in Nuclear Magnetic Resonance Absorption conference, July 2014

The High-Flux Backscattering Spectrometer at the NIST Center for Neutron Research text, January 2002

Glass Transition Phenomenon for Conjugated Polymers journal, April 2019

Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers journal, May 2019

Glass transition temperature from the chemical structure of conjugated polymers journal, February 2020

High Performance Amorphous Polymeric Thin-Film Transistors Based on Poly[(1,2-bis-(2′-thienyl)vinyl-5′,5′′-diyl)- alt -(9,9-dioctylfluorene-2,7-diyl] Semiconductors
journal, May 2008

Effect of Crystallization Kinetics on Microstructure and Charge Transport of Polythiophenes
journal, October 2012

Electrical conductivity and relaxation in poly(3-hexylthiophene)
journal, November 2009

Two-dimensional charge transport in self-organized, high-mobility conjugated polymers
journal, October 1999

Effect of Miscibility and Percolation on Electron Transport in Amorphous Poly(3-Hexylthiophene)/Phenyl- $C_{61}$ -Butyric Acid Methyl Ester Blends
journal, January 2012

Tuning Polythiophene Crystallization through Systematic Side Chain Functionalization
journal, October 2010

Interplay of Surface Chemistry and Ion Content in Nanoparticle-Filled Solid Polymer Electrolytes
journal, May 2014

Functionalized Acenes and Heteroacenes for Organic Electronics
journal, December 2006

Alkyl-Chain-Length-Independent Hole Mobility via Morphological Control with Poly(3-alkylthiophene) Nanofibers
journal, March 2010

Predicting Nematic Phases of Semiflexible Polymers
journal, February 2015

Hydration dependent studies of highly aligned multilayer lipid membranes by neutron scattering
journal, October 2010

A general relationship between disorder, aggregation and charge transport in conjugated polymers
journal, August 2013

Molecular Dynamics of Regioregular Poly(3-hexylthiophene) Investigated by NMR Relaxation and an Interpretation of Temperature Dependent Optical Absorption
journal, January 2010

Glass Transition Temperature of Conjugated Polymers by Oscillatory Shear Rheometry
journal, June 2017

Temperature-Dependent Dynamics of Polyalkylthiophene Conjugated Polymers: A Combined Neutron Scattering and Simulation Study
journal, November 2015

Charge Transport Physics of Conjugated Polymer Field-Effect Transistors
journal, June 2010

The effect of environment on local dynamics of macromolecules
journal, February 2007

Internal Dynamics in SDS Micelles: Neutron Scattering Study
journal, December 2010

Indacenodithiophene Semiconducting Polymers for High-Performance, Air-Stable Transistors
journal, August 2010

The extended Q -range small-angle neutron scattering diffractometer at the SNS
journal, July 2010

Understanding the Microscopic Origin of the Very High Charge Mobility in PBTTT: Tolerance of Thermal Disorder
journal, September 2013

Device Physics of Solution-Processed Organic Field-Effect Transistors
journal, October 2005

Solvatochromism and Conformational Changes in Fully Dissolved Poly(3-alkylthiophene)s
journal, December 2014

The path to ubiquitous and low-cost organic electronic appliances on plastic
journal, April 2004

Predicting Chain Dimensions of Semiflexible Polymers from Dihedral Potentials
journal, September 2014

Dynamics of PEO in Blends with PMMA: Study of the Effects of Blend Composition via Quasi-Elastic Neutron Scattering
journal, May 2008

Liquid-crystalline semiconducting polymers with high charge-carrier mobility
journal, March 2006

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

Effect of Side-Chain Length on the Polymer Chain Dynamics of Poly(alkyl methacrylate)s in Solution
journal, December 2013

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

A Molecular View of Melting in Anhydrous Phospholipidic Membranes
journal, January 2007

GROMACS: A message-passing parallel molecular dynamics implementation
journal, September 1995

Charge Transport in Organic Semiconductors
journal, April 2007

Dynamics of the α relaxation of a glass-forming polymeric system: Dielectric, mechanical, nuclear-magnetic-resonance, and neutron-scattering studies
journal, October 1991

Non-symmetrical dielectric relaxation behaviour arising from a simple empirical decay function
journal, January 1970

High-Lamellar Ordering and Amorphous-Like π-Network in Short-Chain Thiazolothiazole−Thiophene Copolymers Lead to High Mobilities
journal, February 2009

X-ray structural studies of poly(3-alkylthiophenes): an example of an inverse comb
journal, August 1992

Observation of fragile-to-strong dynamic crossover in protein hydration water
journal, June 2006

Effect of Blending with Poly(ethylene oxide) on the Dynamics of Poly(methyl methacrylate): A Quasi-Elastic Neutron Scattering Approach
journal, December 2004

The high-flux backscattering spectrometer at the NIST Center for Neutron Research
journal, May 2003

Interplay of Structure and Dynamics in Functional Macromolecular and Supramolecular Systems As Revealed by Magnetic Resonance Spectroscopy
journal, August 2015

Challenges and Opportunities in the Development of Conjugated Block Copolymers for Photovoltaics
journal, September 2015

Well-defined, high molecular weight poly(3-alkylthiophene)s in thin-film transistors: side chain invariance in field-effect mobility
journal, January 2010

Alkyl chain length dependence of the field-effect carrier mobility in regioregular poly(3-alkylthiophene)s
journal, January 2005

Coarse-grained simulations of the solution-phase self-assembly of poly(3-hexylthiophene) nanostructures
journal, January 2013

Conductivity relaxation and chain motions in conjugated conducting polymers: neutral poly(3-alkylthiophenes)
journal, May 1993

Influence of side-chain length on main- and side-chain dynamics in poly-n-acrylates: A solid-state NMR study
journal, September 2004

Relaxation Effects in Nuclear Magnetic Resonance Absorption
journal, April 1948

Polymer Chain Shape of Poly(3-alkylthiophenes) in Solution Using Small-Angle Neutron Scattering
journal, February 2013

Coarse-Grained Computer Simulations of Polymer/Fullerene Bulk Heterojunctions for Organic Photovoltaic Applications
journal, December 2009

Effect of side chain length on molecular ordering and field-effect mobility in poly(3-alkylthiophene) transistors
journal, December 2006

Ultrathin Body Poly(3-hexylthiophene) Transistors with Improved Short-Channel Performance
journal, February 2013

The measurement of proton-enhanced carbon-13 T1 values by a method which suppresses artifacts
journal, June 1978

Water mobility in a water-soaked nafion® membrane: A high-resolution neutron quasielastic study
journal, March 1982

Functionalized Acenes and Heteroacenes for Organic Electronics
journal, May 2007

Charge Transport in Organic Semiconductors
journal, July 2007

Relaxation Effects in Nuclear Magnetic Resonance Absorption
conference, July 2014

The High-Flux Backscattering Spectrometer at the NIST Center for Neutron Research
text, January 2002

Glass Transition Phenomenon for Conjugated Polymers
journal, April 2019

Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers
journal, May 2019

Glass transition temperature from the chemical structure of conjugated polymers
journal, February 2020