An insight into non-emissive excited states in conjugated polymers

doi:10.1038/ncomms9246

Title: An insight into non-emissive excited states in conjugated polymers

Abstract

Conjugated polymers in the solid state usually exhibit low fluorescence quantum yields, which limit their applications in many areas such as light-emitting diodes. Despite considerable research efforts, the underlying mechanism still remains controversial and elusive. Here, the nature and properties of excited states in the archetypal polythiophene are investigated via aggregates suspended in solvents with different dielectric constants (ε). In relatively polar solvents (ε>~ 3), the aggregates exhibit a low fluorescence quantum yield (QY) of 2–5%, similar to bulk films, however, in relatively nonpolar solvents (ε<~ 3) they demonstrate much higher fluorescence QY up to 20–30%. A series of mixed quantum-classical atomistic simulations illustrate that dielectric induced stabilization of nonradiative charge-transfer (CT) type states can lead to similar drastic reduction in fluorescence QY as seen experimentally. In conclusion, fluorescence lifetime measurement reveals that the CT-type states exist as a competitive channel of the formation of emissive exciton-type states.

Authors:

Hu, Zhongjian ^[1]; Willard, Adam P. ^[1]; Ono, Robert J. ^[1]; Bielawski, Christopher W. ^[1]; Rossky, Peter J. ^[1];

^[1]

Univ. of Texas at Austin, Austin, TX (United States)

Publication Date:: 2015-09-22

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST); Univ. of Texas at Austin, Austin, TX (United States)

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

OSTI Identifier:: 1459344

Grant/Contract Number:: SC0001091

Resource Type:: Accepted Manuscript

Journal Name:: Nature Communications

Additional Journal Information:: Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2041-1723

Publisher:: Nature Publishing Group

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Hu, Zhongjian, Willard, Adam P., Ono, Robert J., Bielawski, Christopher W., Rossky, Peter J., and Vanden Bout, David A. An insight into non-emissive excited states in conjugated polymers.  United States: N. p., 2015. 
        Web.  doi:10.1038/ncomms9246.

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                    Hu, Zhongjian, Willard, Adam P., Ono, Robert J., Bielawski, Christopher W., Rossky, Peter J., & Vanden Bout, David A. An insight into non-emissive excited states in conjugated polymers.  United States.  doi:10.1038/ncomms9246.

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                    Hu, Zhongjian, Willard, Adam P., Ono, Robert J., Bielawski, Christopher W., Rossky, Peter J., and Vanden Bout, David A. Tue .  
        "An insight into non-emissive excited states in conjugated polymers".  United States.  doi:10.1038/ncomms9246.  https://www.osti.gov/servlets/purl/1459344.

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@article{osti_1459344,

  title        = {An insight into non-emissive excited states in conjugated polymers},

  author       = {Hu, Zhongjian and Willard, Adam P. and Ono, Robert J. and Bielawski, Christopher W. and Rossky, Peter J. and Vanden Bout, David A.},

  abstractNote = {Conjugated polymers in the solid state usually exhibit low fluorescence quantum yields, which limit their applications in many areas such as light-emitting diodes. Despite considerable research efforts, the underlying mechanism still remains controversial and elusive. Here, the nature and properties of excited states in the archetypal polythiophene are investigated via aggregates suspended in solvents with different dielectric constants (ε). In relatively polar solvents (ε>~ 3), the aggregates exhibit a low fluorescence quantum yield (QY) of 2–5%, similar to bulk films, however, in relatively nonpolar solvents (ε<~ 3) they demonstrate much higher fluorescence QY up to 20–30%. A series of mixed quantum-classical atomistic simulations illustrate that dielectric induced stabilization of nonradiative charge-transfer (CT) type states can lead to similar drastic reduction in fluorescence QY as seen experimentally. In conclusion, fluorescence lifetime measurement reveals that the CT-type states exist as a competitive channel of the formation of emissive exciton-type states.},

  doi          = {10.1038/ncomms9246},

  journal      = {Nature Communications},

  number       = 1,

  volume       = 6,

  place        = {United States},

  year         = {2015},

  month        = {9}

}

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DOI: 10.1038/ncomms9246

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Similar Records

Title: An insight into non-emissive excited states in conjugated polymers

Abstract

Citation Formats

Excited-State Dynamics and Self-Organization of Poly(3-hexylthiophene) (P3HT) in Solution and Thin Films journal, February 2012

Highly Ordered Single Conjugated Polymer Chain Rod Morphologies journal, October 2010

Effect of Conjugated Backbone Protection on Intrinsic and Light-Induced Fluorescence Quenching in Polythiophenes journal, August 2014

Singlet-Triplet Annihilation Limits Exciton Yield in Poly(3-Hexylthiophene) journal, April 2014

Extraction of poly (3-hexylthiophene) (P3HT) properties from dark current voltage characteristics in a P3HT/n-crystalline-silicon solar cell journal, February 2010

Ultrafast photogeneration of inter-chain charge pairs in polythiophene films journal, May 2000

Analysis of the excited states of regioregular polythiophene P3HT journal, January 2008

Computer Simulation of the Excited State Dynamics of Betaine-30 in Acetonitrile journal, November 1999

Microscopic calculations of solvent effects on absorption spectra of conjugated molecules journal, June 1991

Utopia dielectrica journal, February 1995

Nonadiabatic Simulations of Exciton Dissociation in Poly- p -phenylenevinylene Oligomers journal, July 2010

What is the effective dielectric constant in a β-cyclodextrin cavity? Insights from Molecular Dynamics simulations and QM/MM calculations journal, August 2011

Maximizing Singlet Fission by Intermolecular Packing journal, September 2014

The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates journal, March 2010

Designing J- and H-Aggregates through Wave Function Overlap Engineering: Applications to Poly(3-hexylthiophene) journal, November 2012

Charge Separation in Semicrystalline Polymeric Semiconductors by Photoexcitation: Is the Mechanism Intrinsic or Extrinsic? journal, May 2011

Preparation and Characterization of Water Self-dispersible Poly(3-hexylthiophene) Particles journal, November 2007

Effect of Polymer Chain Folding on the Transition from H- to J-Aggregate Behavior in P3HT Nanofibers journal, January 2014

Calculation of ground and excited state potential surfaces of conjugated molecules. I. Formulation and parametrization journal, August 1972

J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers journal, January 2012

Aggregation Behavior of Rod–Coil–Rod Triblock Copolymers in a Coil-Selective Solvent journal, December 2014

Conducting Polymer Material Characterization Using High Frequency Planar Transmission Line Measurement journal, October 2012

Light-Emitting Polythiophenes journal, October 2005

A polymer tandem solar cell with 10.6% power conversion efficiency journal, February 2013

Synthesis, Properties, and Electronic Applications of Size-Controlled Poly(3-hexylthiophene) Nanoparticles journal, August 2010

Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene journal, May 2007

Mimicking Conjugated Polymer Thin-Film Photophysics with a Well-Defined Triblock Copolymer in Solution journal, February 2012

Electric contacts on conductive polymers: sodium on poly(3-hexylthiophene-2,5-diyl) journal, March 2002

Modeling disorder in polymer aggregates: The optical spectroscopy of regioregular poly(3-hexylthiophene) thin films journal, June 2005

A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene:fullerene solar cells journal, February 2006

Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities journal, November 2009

Charge-transfer excitons in strongly coupled organic semiconductors journal, January 2010

Charge Photogeneration in Neat Conjugated Polymers journal, September 2013

Fate of Excitations in Conjugated Polymers: Single-Molecule Spectroscopy Reveals Nonemissive “Dark” Regions in MEH-PPV Individual Chains journal, December 2009

Recent advances in transistor performance of polythiophenes journal, December 2013

Statistical accuracy in fluorescence correlation spectroscopy journal, December 1974

Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model journal, May 2012

MIS polymeric structures and OTFTs using PMMA on P3HT layers journal, January 2008

Molecular Modeling and Simulation of Conjugated Polymer Oligomers: Ground and Excited State Chain Dynamics of PPV in the Gas Phase journal, April 2008

Experimental determination of the charge/neutral branching ratio η in the photoexcitation of π -conjugated polymers by broadband ultrafast spectroscopy journal, February 2007

Electronic Energy Transfer and Quantum-Coherence in π-Conjugated Polymers † journal, February 2011

A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. II journal, May 1953

Electron interaction in unsaturated hydrocarbons journal, January 1953

Chromism and luminescence in regioregular poly(3-dodecylthiophene) journal, January 1996

Mixed Quantum-Classical Description of Excitation Energy Transfer in Supramolecular Complexes: Screening of the Excitonic Coupling journal, January 2014

PCBM concentration dependent morphology of P3HT in composite P3HT/PCBM nanoparticles journal, July 2009

Insights into Excitons Confined to Nanoscale Systems: Electron–Hole Interaction, Binding Energy, and Photodissociation journal, February 2008

Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics journal, December 2012

Controlling microstructure in poly(3-hexylthiophene) nanofibers journal, January 2012

Polymer solar cells journal, February 2012

Molecular Packing in Organic Solar Cell Materials: Insights from the Emission Line Shapes of P3HT/PCBM Polymer Blend Nanoparticles journal, August 2014

How Solvent Controls Electronic Energy Transfer and Light Harvesting: Toward a Quantum-Mechanical Description of Reaction Field and Screening Effects journal, November 2007

Role of Ultrafast Torsional Relaxation in the Emission from Polythiophene Aggregates journal, September 2010

Impedance Spectroscopy on Polymer-Fullerene Solar Cells journal, January 2007

Solvent and Intramolecular Effects on the Absorption Spectrum of Betaine-30 journal, February 2000

Photophysics of Substituted Polythiophenes journal, September 1999

Photogeneration and Ultrafast Dynamics of Excitons and Charges in P3HT/PCBM Blends journal, July 2009

A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. I. journal, March 1953

Conformation and Energy Transfer in Single Conjugated Polymers journal, March 2012

Control of aggregate formation in poly(3-hexylthiophene) by solvent, molecular weight, and synthetic method journal, December 2011

Effect of the Side-Chain-Distribution Density on the Single-Conjugated-Polymer-Chain Conformation journal, November 2013

Remarkable Mechanochromism in Blends of a π‐Conjugated Polymer P3TEOT: The Role of Conformational Transitions and Aggregation journal, November 2019

A de novo strategy for predictive crystal engineering to tune excitonic coupling journal, May 2019

Impact of backbone fluorination on nanoscale morphology and excitonic coupling in polythiophenes journal, May 2017

A π-conjugated, covalent phosphinine framework text, January 2019

Modeling the effects of molecular disorder on the properties of Frenkel excitons in organic molecular semiconductors journal, September 2018

Energetics of exciton binding and dissociation in polythiophenes: a tight binding approach journal, January 2019

Excited-State Dynamics and Self-Organization of Poly(3-hexylthiophene) (P3HT) in Solution and Thin Films
journal, February 2012

Highly Ordered Single Conjugated Polymer Chain Rod Morphologies
journal, October 2010

Effect of Conjugated Backbone Protection on Intrinsic and Light-Induced Fluorescence Quenching in Polythiophenes
journal, August 2014

Singlet-Triplet Annihilation Limits Exciton Yield in Poly(3-Hexylthiophene)
journal, April 2014

Extraction of poly (3-hexylthiophene) (P3HT) properties from dark current voltage characteristics in a P3HT/n-crystalline-silicon solar cell
journal, February 2010

Ultrafast photogeneration of inter-chain charge pairs in polythiophene films
journal, May 2000

Analysis of the excited states of regioregular polythiophene P3HT
journal, January 2008

Computer Simulation of the Excited State Dynamics of Betaine-30 in Acetonitrile
journal, November 1999

Microscopic calculations of solvent effects on absorption spectra of conjugated molecules
journal, June 1991

Utopia dielectrica
journal, February 1995

Nonadiabatic Simulations of Exciton Dissociation in Poly- p -phenylenevinylene Oligomers
journal, July 2010

What is the effective dielectric constant in a β-cyclodextrin cavity? Insights from Molecular Dynamics simulations and QM/MM calculations
journal, August 2011

Maximizing Singlet Fission by Intermolecular Packing
journal, September 2014

The Spectral Signatures of Frenkel Polarons in H- and J-Aggregates
journal, March 2010

Designing J- and H-Aggregates through Wave Function Overlap Engineering: Applications to Poly(3-hexylthiophene)
journal, November 2012

Charge Separation in Semicrystalline Polymeric Semiconductors by Photoexcitation: Is the Mechanism Intrinsic or Extrinsic?
journal, May 2011

Preparation and Characterization of Water Self-dispersible Poly(3-hexylthiophene) Particles
journal, November 2007

Effect of Polymer Chain Folding on the Transition from H- to J-Aggregate Behavior in P3HT Nanofibers
journal, January 2014

Calculation of ground and excited state potential surfaces of conjugated molecules. I. Formulation and parametrization
journal, August 1972

J-Aggregate Behavior in Poly-3-hexylthiophene Nanofibers
journal, January 2012

Aggregation Behavior of Rod–Coil–Rod Triblock Copolymers in a Coil-Selective Solvent
journal, December 2014

Conducting Polymer Material Characterization Using High Frequency Planar Transmission Line Measurement
journal, October 2012

Light-Emitting Polythiophenes
journal, October 2005

A polymer tandem solar cell with 10.6% power conversion efficiency
journal, February 2013

Synthesis, Properties, and Electronic Applications of Size-Controlled Poly(3-hexylthiophene) Nanoparticles
journal, August 2010

Role of Intermolecular Coupling in the Photophysics of Disordered Organic Semiconductors: Aggregate Emission in Regioregular Polythiophene
journal, May 2007

Mimicking Conjugated Polymer Thin-Film Photophysics with a Well-Defined Triblock Copolymer in Solution
journal, February 2012

Electric contacts on conductive polymers: sodium on poly(3-hexylthiophene-2,5-diyl)
journal, March 2002

Modeling disorder in polymer aggregates: The optical spectroscopy of regioregular poly(3-hexylthiophene) thin films
journal, June 2005

A strong regioregularity effect in self-organizing conjugated polymer films and high-efficiency polythiophene:fullerene solar cells
journal, February 2006

Near-IR Femtosecond Transient Absorption Spectroscopy of Ultrafast Polaron and Triplet Exciton Formation in Polythiophene Films with Different Regioregularities
journal, November 2009

Charge-transfer excitons in strongly coupled organic semiconductors
journal, January 2010

Charge Photogeneration in Neat Conjugated Polymers
journal, September 2013

Fate of Excitations in Conjugated Polymers: Single-Molecule Spectroscopy Reveals Nonemissive “Dark” Regions in MEH-PPV Individual Chains
journal, December 2009

Recent advances in transistor performance of polythiophenes
journal, December 2013

Statistical accuracy in fluorescence correlation spectroscopy
journal, December 1974

Interplay between intrachain and interchain interactions in semiconducting polymer assemblies: The HJ-aggregate model
journal, May 2012

MIS polymeric structures and OTFTs using PMMA on P3HT layers
journal, January 2008

Molecular Modeling and Simulation of Conjugated Polymer Oligomers: Ground and Excited State Chain Dynamics of PPV in the Gas Phase
journal, April 2008

Experimental determination of the charge/neutral branching ratio $η$ in the photoexcitation of $π$ -conjugated polymers by broadband ultrafast spectroscopy
journal, February 2007

Electronic Energy Transfer and Quantum-Coherence in π-Conjugated Polymers ^†
journal, February 2011

A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. II
journal, May 1953

Electron interaction in unsaturated hydrocarbons
journal, January 1953

Chromism and luminescence in regioregular poly(3-dodecylthiophene)
journal, January 1996

Mixed Quantum-Classical Description of Excitation Energy Transfer in Supramolecular Complexes: Screening of the Excitonic Coupling
journal, January 2014

PCBM concentration dependent morphology of P3HT in composite P3HT/PCBM nanoparticles
journal, July 2009

Insights into Excitons Confined to Nanoscale Systems: Electron–Hole Interaction, Binding Energy, and Photodissociation
journal, February 2008

Hot charge-transfer excitons set the time limit for charge separation at donor/acceptor interfaces in organic photovoltaics
journal, December 2012

Controlling microstructure in poly(3-hexylthiophene) nanofibers
journal, January 2012

Polymer solar cells
journal, February 2012

Molecular Packing in Organic Solar Cell Materials: Insights from the Emission Line Shapes of P3HT/PCBM Polymer Blend Nanoparticles
journal, August 2014

How Solvent Controls Electronic Energy Transfer and Light Harvesting: Toward a Quantum-Mechanical Description of Reaction Field and Screening Effects
journal, November 2007

Role of Ultrafast Torsional Relaxation in the Emission from Polythiophene Aggregates
journal, September 2010

Impedance Spectroscopy on Polymer-Fullerene Solar Cells
journal, January 2007

Solvent and Intramolecular Effects on the Absorption Spectrum of Betaine-30
journal, February 2000

Photophysics of Substituted Polythiophenes
journal, September 1999

Photogeneration and Ultrafast Dynamics of Excitons and Charges in P3HT/PCBM Blends
journal, July 2009

A Semi‐Empirical Theory of the Electronic Spectra and Electronic Structure of Complex Unsaturated Molecules. I.
journal, March 1953

Conformation and Energy Transfer in Single Conjugated Polymers
journal, March 2012

Control of aggregate formation in poly(3-hexylthiophene) by solvent, molecular weight, and synthetic method
journal, December 2011

Effect of the Side-Chain-Distribution Density on the Single-Conjugated-Polymer-Chain Conformation
journal, November 2013

Remarkable Mechanochromism in Blends of a π‐Conjugated Polymer P3TEOT: The Role of Conformational Transitions and Aggregation
journal, November 2019

A de novo strategy for predictive crystal engineering to tune excitonic coupling
journal, May 2019

Impact of backbone fluorination on nanoscale morphology and excitonic coupling in polythiophenes
journal, May 2017

A π-conjugated, covalent phosphinine framework
text, January 2019

Modeling the effects of molecular disorder on the properties of Frenkel excitons in organic molecular semiconductors
journal, September 2018

Energetics of exciton binding and dissociation in polythiophenes: a tight binding approach
journal, January 2019