skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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:
 [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Texas at Austin, Austin, TX (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Understanding Charge Separation and Transfer at Interfaces in Energy Materials (CST); Univ. of Texas, 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. https://doi.org/10.1038/ncomms9246.
Copy to clipboard
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. https://doi.org/10.1038/ncomms9246
Copy to clipboard
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. https://doi.org/10.1038/ncomms9246. https://www.osti.gov/servlets/purl/1459344.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1038/ncomms9246
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 29 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

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

  • Ferreira, Bruno; da Silva, Palmira Ferreira; Seixas de Melo, J. Sérgio
  • The Journal of Physical Chemistry B, Vol. 116, Issue 8
  • DOI: 10.1021/jp207418q

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

  • Adachi, Takuji; Brazard, Johanna; Chokshi, Paresh
  • The Journal of Physical Chemistry C, Vol. 114, Issue 48
  • DOI: 10.1021/jp108546w

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

  • Sahoo, Dibakar; Sugiyasu, Kazunori; Tian, Yuxi
  • Chemistry of Materials, Vol. 26, Issue 16
  • DOI: 10.1021/cm5021959

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

  • Nolasco, J. C.; Cabré, R.; Ferré-Borrull, J.
  • Journal of Applied Physics, Vol. 107, Issue 4
  • DOI: 10.1063/1.3296294

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

  • Cook, Steffan; Furube, Akihiro; Katoh, Ryuzi
  • Energy & Environmental Science, Vol. 1, Issue 2
  • DOI: 10.1039/b805643a

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

  • Lobaugh, John; Rossky, Peter J.
  • The Journal of Physical Chemistry A, Vol. 103, Issue 47
  • DOI: 10.1021/jp991604w

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

  • Luzhkov, V.; Warshel, A.
  • Journal of the American Chemical Society, Vol. 113, Issue 12
  • DOI: 10.1021/ja00012a018

Utopia dielectrica
journal, February 1995

  • Van Duijnen, Piet Th.; De Vries, Alex H.
  • International Journal of Quantum Chemistry, Vol. 56, Issue S29
  • DOI: 10.1002/qua.560560855

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

  • Bedard-Hearn, Michael J.; Sterpone, Fabio; Rossky, Peter J.
  • The Journal of Physical Chemistry A, Vol. 114, Issue 29
  • DOI: 10.1021/jp103446z

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

  • Lambert, Alexandrine; Yeguas, Violeta; Monard, Gérald
  • Computational and Theoretical Chemistry, Vol. 968, Issue 1-3
  • DOI: 10.1016/j.comptc.2011.05.008

Maximizing Singlet Fission by Intermolecular Packing
journal, September 2014

  • Wang, Linjun; Olivier, Yoann; Prezhdo, Oleg V.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 19
  • DOI: 10.1021/jz5015955

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

  • Spano, Frank C.
  • Accounts of Chemical Research, Vol. 43, Issue 3
  • DOI: 10.1021/ar900233v

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

  • Yamagata, Hajime; Pochas, Chris M.; Spano, Frank C.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 49
  • DOI: 10.1021/jp309407r

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

  • Baghgar, Mina; Labastide, Joelle A.; Bokel, Felicia
  • The Journal of Physical Chemistry C, Vol. 118, Issue 4
  • DOI: 10.1021/jp411668g

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

  • Warshel, A.; Karplus, M.
  • Journal of the American Chemical Society, Vol. 94, Issue 16
  • DOI: 10.1021/ja00771a014

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

  • Niles, Edwards T.; Roehling, John D.; Yamagata, Hajime
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 2
  • DOI: 10.1021/jz201509h

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

  • Omar, Ahmad K.; Hanson, Ben; Haws, Ryan T.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 1
  • DOI: 10.1021/jp509016c

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

  • Cho, Young-Seek; Franklin, Rhonda R.
  • Transactions on Electrical and Electronic Materials, Vol. 13, Issue 5
  • DOI: 10.4313/TEEM.2012.13.5.237

Light-Emitting Polythiophenes
journal, October 2005

  • Perepichka, I. F.; Perepichka, D. F.; Meng, H.
  • Advanced Materials, Vol. 17, Issue 19
  • DOI: 10.1002/adma.200500461

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

  • You, Jingbi; Dou, Letian; Yoshimura, Ken
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2411

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

  • Millstone, Jill E.; Kavulak, David F. J.; Woo, Claire H.
  • Langmuir, Vol. 26, Issue 16, p. 13056-13061
  • DOI: 10.1021/la1022938

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

  • Brazard, Johanna; Ono, Robert J.; Bielawski, Christopher W.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 16
  • DOI: 10.1021/jp3001256

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

  • Spano, Frank C.
  • The Journal of Chemical Physics, Vol. 122, Issue 23
  • DOI: 10.1063/1.1914768

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

  • Kim, Youngkyoo; Cook, Steffan; Tuladhar, Sachetan M.
  • Nature Materials, Vol. 5, Issue 3
  • DOI: 10.1038/nmat1574

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

  • Guo, Jiamo; Ohkita, Hideo; Benten, Hiroaki
  • Journal of the American Chemical Society, Vol. 131, Issue 46
  • DOI: 10.1021/ja906621a

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

Charge Photogeneration in Neat Conjugated Polymers
journal, September 2013

  • Reid, Obadiah G.; Pensack, Ryan D.; Song, Yin
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4027144

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

  • Lin, Hongzhen; Tian, Yuxi; Zapadka, Karolina
  • Nano Letters, Vol. 9, Issue 12
  • DOI: 10.1021/nl9027473

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

  • Yamagata, H.; Spano, F. C.
  • The Journal of Chemical Physics, Vol. 136, Issue 18
  • DOI: 10.1063/1.4705272

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

  • Sterpone, Fabio; Rossky, Peter J.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 16
  • DOI: 10.1021/jp711848q

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

  • Hwang, Inchan; Scholes, Gregory D.
  • Chemistry of Materials, Vol. 23, Issue 3
  • DOI: 10.1021/cm102360x

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

  • Pariser, Rudolph; Parr, Robert G.
  • The Journal of Chemical Physics, Vol. 21, Issue 5
  • DOI: 10.1063/1.1699030

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

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

  • Jailaubekov, Askat E.; Willard, Adam P.; Tritsch, John R.
  • Nature Materials, Vol. 12, Issue 1
  • DOI: 10.1038/nmat3500

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

  • Roehling, John D.; Arslan, Ilke; Moulé, Adam J.
  • J. Mater. Chem., Vol. 22, Issue 6
  • DOI: 10.1039/C2JM13633C

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

  • Crotty, Angela M.; Gizzi, Alicia N.; Rivera-Jacquez, Hector J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 34
  • DOI: 10.1021/jp5040932

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

  • Curutchet, Carles; Scholes, Gregory D.; Mennucci, Benedetta
  • The Journal of Physical Chemistry B, Vol. 111, Issue 46
  • DOI: 10.1021/jp075411h

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

  • Parkinson, Patrick; Müller, Christian; Stingelin, Natalie
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 19
  • DOI: 10.1021/jz101026g

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

  • Knipper, Martin; Parisi, Jürgen; Coakley, Kevin
  • Zeitschrift für Naturforschung A, Vol. 62, Issue 9
  • DOI: 10.1515/zna-2007-0904

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

  • Lobaugh, John; Rossky, Peter J.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 5
  • DOI: 10.1021/jp993444u

Photophysics of Substituted Polythiophenes
journal, September 1999

  • Theander, Mathias; Inganäs, Olle; Mammo, Wendimagen
  • The Journal of Physical Chemistry B, Vol. 103, Issue 37
  • DOI: 10.1021/jp983684u

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

  • Piris, Jorge; Dykstra, Tieneke E.; Bakulin, Artem A.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 32
  • DOI: 10.1021/jp904229q

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

  • Pariser, Rudolph; Parr, Robert G.
  • The Journal of Chemical Physics, Vol. 21, Issue 3
  • DOI: 10.1063/1.1698929

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

  • Bolinger, Joshua C.; Traub, Matthew C.; Brazard, Johanna
  • Accounts of Chemical Research, Vol. 45, Issue 11
  • DOI: 10.1021/ar300012k

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

  • Scharsich, Christina; Lohwasser, Ruth H.; Sommer, Michael
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 6
  • DOI: 10.1002/polb.23022

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

    [ × clear filter / sort ]

    Works referencing / citing this record:

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

    • Zessin, Johanna; Schnepf, Max; Oertel, Ulrich
    • Advanced Optical Materials, Vol. 8, Issue 2
    • DOI: 10.1002/adom.201901410

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

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

    • Bombile, Joel H.; Janik, Michael J.; Milner, Scott T.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 22
    • DOI: 10.1039/c9cp01116a

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

    • Shi, Liang; Willard, Adam P.
    • The Journal of Chemical Physics, Vol. 149, Issue 9
    • DOI: 10.1063/1.5044553

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

    • Hu, Zhongjian; Haws, Ryan T.; Fei, Zhuping
    • Proceedings of the National Academy of Sciences, Vol. 114, Issue 20
    • DOI: 10.1073/pnas.1620722114

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

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

    A de novo strategy for predictive crystal engineering to tune excitonic coupling
    text, January 2019

    A π‐Conjugated, Covalent Phosphinine Framework
    journal, August 2019

    • Huang, Jieyang; Tarábek, Ján; Kulkarni, Ranjit
    • Chemistry – A European Journal, Vol. 25, Issue 53
    • DOI: 10.1002/chem.201900281
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: