Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps

Abstract

Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, andmore » that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.« less

Authors:
 [1];  [1];  [2];  [3];  [4];  [2];  [2];  [2]
+ Show Author Affiliations
  1. Dowling College, Oakdale, NY (United States); Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Dowling College, Oakdale, NY (United States)
  4. Kyoto Inst. of Technology, Kyoto (Japan)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1214521
Report Number(s):
BNL-108317-2015-JA
Journal ID: ISSN 1520-6106; R&D Project: CO004; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B
Additional Journal Information:
Journal Volume: 119; Journal Issue: 24; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; exciton trapping; charge transfer state; conjugated polymer; polyfluorene; exciton diffusion; diffusion length; charge transfer exciton

Citation Formats

Zaikowski, Lori, Mauro, Gina, Bird, Matthew, Karten, Brianne, Asaoka, Sadayuki, Wu, Qin, Cook, Andrew R., and Miller, John R. Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps. United States: N. p., 2014. Web. doi:10.1021/jp510095p.
Copy to clipboard
Zaikowski, Lori, Mauro, Gina, Bird, Matthew, Karten, Brianne, Asaoka, Sadayuki, Wu, Qin, Cook, Andrew R., & Miller, John R. Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps. United States. https://doi.org/10.1021/jp510095p
Copy to clipboard
Zaikowski, Lori, Mauro, Gina, Bird, Matthew, Karten, Brianne, Asaoka, Sadayuki, Wu, Qin, Cook, Andrew R., and Miller, John R. Mon . "Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps". United States. https://doi.org/10.1021/jp510095p. https://www.osti.gov/servlets/purl/1214521.
Copy to clipboard
@article{osti_1214521,
title = {Charge transfer fluorescence and 34 nm exciton diffusion length in polymers with electron acceptor end traps},
author = {Zaikowski, Lori and Mauro, Gina and Bird, Matthew and Karten, Brianne and Asaoka, Sadayuki and Wu, Qin and Cook, Andrew R. and Miller, John R.},
abstractNote = {Photoexcitation of conjugated poly-2,7-(9,9-dihexylfluorene) polyfluorenes with naphthylimide (NI) and anthraquinone (AQ) electron-acceptor end traps produces excitons that form charge transfer states at the end traps. Intramolecular singlet exciton transport to end traps was examined by steady state fluorescence for polyfluorenes of 17 to 127 repeat units in chloroform, dimethylformamide (DMF), tetrahydrofuran (THF), and p-xylene. End traps capture excitons and form charge transfer (CT) states at all polymer lengths and in all solvents. The CT nature of the end-trapped states is confirmed by their fluorescence spectra, solvent and trap group dependence and DFT descriptions. Quantum yields of CT fluorescence are as large as 46%. This strong CT emission is understood in terms of intensity borrowing. Energies of the CT states from onsets of the fluorescence spectra give the depths of the traps which vary with solvent polarity. For NI end traps the trap depths are 0.06 (p-xylene), 0.13 (THF) and 0.19 eV (CHCl3). For AQ, CT fluorescence could be observed only in p-xylene where the trap depth is 0.27 eV. Quantum yields, emission energies, charge transfer energies, solvent reorganization and vibrational energies were calculated. Fluorescence measurements on chains >100 repeat units indicate that end traps capture ~50% of the excitons, and that the exciton diffusion length LD =34 nm, which is much larger than diffusion lengths reported in polymer films or than previously known for diffusion along isolated chains. As a result, the efficiency of exciton capture depends on chain length, but not on trap depth, solvent polarity or which trap group is present.},
doi = {10.1021/jp510095p},
journal = {Journal of Physical Chemistry. B},
number = 24,
volume = 119,
place = {United States},
year = {Mon Dec 22 00:00:00 EST 2014},
month = {Mon Dec 22 00:00:00 EST 2014}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/jp510095p
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 15 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:

Assessment of a long-range corrected hybrid functional
journal, December 2006

  • Vydrov, Oleg A.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 125, Issue 23
  • DOI: 10.1063/1.2409292

Polyfluorene Derivatives:  Effective Conjugation Lengths from Well-Defined Oligomers
journal, March 1998

  • Klaerner, G.; Miller, R. D.
  • Macromolecules, Vol. 31, Issue 6
  • DOI: 10.1021/ma971073e

Principles of Fluorescence Spectroscopy
book, January 2006

Exciton diffusion length in narrow bandgap polymers
journal, January 2012

  • Mikhnenko, Oleksandr V.; Azimi, Hamed; Scharber, Markus
  • Energy & Environmental Science, Vol. 5, Issue 5
  • DOI: 10.1039/c2ee03466b

Absolute Rate of Charge Separation and Recombination in a Molecular Model of the P3HT/PCBM Interface
journal, December 2010

  • Liu, Tao; Troisi, Alessandro
  • The Journal of Physical Chemistry C, Vol. 115, Issue 5
  • DOI: 10.1021/jp109130y

A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution
journal, August 2006

  • Improta, Roberto; Barone, Vincenzo; Scalmani, Giovanni
  • The Journal of Chemical Physics, Vol. 125, Issue 5
  • DOI: 10.1063/1.2222364

Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory
journal, July 1996

Effects of optical interference and energy transfer on exciton diffusion length measurements in organic semiconductors
journal, August 2006

  • Scully, Shawn R.; McGehee, Michael D.
  • Journal of Applied Physics, Vol. 100, Issue 3
  • DOI: 10.1063/1.2226687

Conjugated “Molecular Wire” for Excitons
journal, April 2010

  • Shibano, Yuki; Imahori, Hiroshi; Sreearunothai, Paiboon
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 9
  • DOI: 10.1021/jz100380m

Toward effective and reliable fluorescence energies in solution by a new state specific polarizable continuum model time dependent density functional theory approach
journal, August 2007

  • Improta, Roberto; Scalmani, Giovanni; Frisch, Michael J.
  • The Journal of Chemical Physics, Vol. 127, Issue 7
  • DOI: 10.1063/1.2757168

Role of Bad Dihedral Angles: Methylfluorenes Act as Energy Barriers for Excitons and Polarons of Oligofluorenes
journal, September 2014

  • Mani, Tomoyasu; Miller, John R.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 40
  • DOI: 10.1021/jp5080626

Continuous surface charge polarizable continuum models of solvation. I. General formalism
journal, March 2010

  • Scalmani, Giovanni; Frisch, Michael J.
  • The Journal of Chemical Physics, Vol. 132, Issue 11
  • DOI: 10.1063/1.3359469

Time-Dependent Density Functional Response Theory for Molecules
book, November 1995

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

Exciton Diffusion Measurements in Poly(3-hexylthiophene)
journal, July 2008

  • Shaw, Paul E.; Ruseckas, Arvydas; Samuel, Ifor D. W.
  • Advanced Materials, Vol. 20, Issue 18, p. 3516-3520
  • DOI: 10.1002/adma.200800982

Electron and Hole Transport To Trap Groups at the Ends of Conjugated Polyfluorenes
journal, September 2008

  • Asaoka, Sadayuki; Takeda, Norihiko; Iyoda, Tomokazu
  • Journal of the American Chemical Society, Vol. 130, Issue 36
  • DOI: 10.1021/ja800426z

Optical and thermal electron transfer in rigid difunctional molecules of fixed distance and orientation
journal, August 1987

  • Penfield, K. W.; Miller, J. R.; Paddon-Row, M. N.
  • Journal of the American Chemical Society, Vol. 109, Issue 17
  • DOI: 10.1021/ja00251a001

One-Dimensional Singlet Exciton Diffusion in Poly(3-hexylthiophene) Crystalline Domains
journal, January 2014

  • Tamai, Yasunari; Matsuura, Yuu; Ohkita, Hideo
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 2
  • DOI: 10.1021/jz402299a

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

Intramolecular Exciton Diffusion in Poly(3-hexylthiophene)
journal, September 2013

  • Healy, Andrew T.; Boudouris, Bryan W.; Frisbie, C. Daniel
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 20
  • DOI: 10.1021/jz401694j

Efficient photodiodes from interpenetrating polymer networks
journal, August 1995

  • Halls, J. J. M.; Walsh, C. A.; Greenham, N. C.
  • Nature, Vol. 376, Issue 6540, p. 498-500
  • DOI: 10.1038/376498a0

Geometries and properties of excited states in the gas phase and in solution: Theory and application of a time-dependent density functional theory polarizable continuum model
journal, March 2006

  • Scalmani, Giovanni; Frisch, Michael J.; Mennucci, Benedetta
  • The Journal of Chemical Physics, Vol. 124, Issue 9
  • DOI: 10.1063/1.2173258

Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions
journal, December 1995

Transport of Triplet Excitons along Continuous 100 nm Polyfluorene Chains
journal, December 2014

  • Li, Xiang; Bird, Matthew; Mauro, Gina
  • The Journal of Physical Chemistry B, Vol. 119, Issue 24
  • DOI: 10.1021/jp509396s

Low bandgap polymers for photon harvesting in bulk heterojunction solar cells
journal, January 2004

  • Winder, Christoph; Sariciftci, Niyazi Serdar
  • Journal of Materials Chemistry, Vol. 14, Issue 7
  • DOI: 10.1039/b306630d

Simultaneous enhancement of charge transport and exciton diffusion in poly( p -phenylene vinylene) derivatives
journal, July 2005

Ab Initio Study of the Emissive Charge-Transfer States of Solvated Chromophore-Functionalized Silsesquioxanes
journal, April 2012

  • Zheng, Shaohui; Phillips, Heidi; Geva, Eitan
  • Journal of the American Chemical Society, Vol. 134, Issue 16
  • DOI: 10.1021/ja301442v

Triplet Transport to and Trapping by Acceptor End Groups on Conjugated Polyfluorene Chains
journal, September 2011

  • Sreearunothai, Paiboon; Estrada, Alexis; Asaoka, Sadayuki
  • The Journal of Physical Chemistry C, Vol. 115, Issue 40
  • DOI: 10.1021/jp205828q

Singlet exciton diffusion in MEH-PPV films studied by exciton–exciton annihilation
journal, December 2006

Temperature Dependence of Exciton Diffusion in Conjugated Polymers
journal, September 2008

  • Mikhnenko, O. V.; Cordella, F.; Sieval, A. B.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 37
  • DOI: 10.1021/jp8042363

Delayed Luminescence Induced by Multiple Photon Excitation of Ground Electronic State Polyatomic Molecules with CO 2 Laser
journal, April 1990

  • Borisevich, N. A.; Zalesskaya, G. A.; Urbanovich, A. E.
  • Spectroscopy Letters, Vol. 23, Issue 4
  • DOI: 10.1080/00387019008054424

Photophysical characterization of dilute solutions and ordered thin films of alkyl-substituted polyfluorenes
journal, January 1999

  • Teetsov, Julie; Fox, Marye Anne
  • Journal of Materials Chemistry, Vol. 9, Issue 9
  • DOI: 10.1039/a902829c

Lifetimes for Radiative Charge Recombination in Donor-Acceptor Molecules
journal, August 1994

  • Bixon, M.; Jortner, Joshua; Verhoeven, Jan W.
  • Journal of the American Chemical Society, Vol. 116, Issue 16
  • DOI: 10.1021/ja00095a044

Exciton Migration in Rigid-Rod Conjugated Polymers:  An Improved Förster Model
journal, April 2005

  • Hennebicq, Emmanuelle; Pourtois, Geoffrey; Scholes, Gregory D.
  • Journal of the American Chemical Society, Vol. 127, Issue 13
  • DOI: 10.1021/ja0488784

Polarons, Bipolarons, and Side-By-Side Polarons in Reduction of Oligofluorenes
journal, June 2012

  • Zaikowski, Lori; Kaur, Parmeet; Gelfond, Claudia
  • Journal of the American Chemical Society, Vol. 134, Issue 26
  • DOI: 10.1021/ja301494n

Exciton Dynamics in Disordered Poly( p -phenylenevinylene). 2. Exciton Diffusion
journal, October 2012

  • Barford, William; Bittner, Eric R.; Ward, Alec
  • The Journal of Physical Chemistry A, Vol. 116, Issue 42
  • DOI: 10.1021/jp307041n

Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers
journal, August 2002

  • Beljonne, D.; Pourtois, G.; Silva, C.
  • Proceedings of the National Academy of Sciences, Vol. 99, Issue 17
  • DOI: 10.1073/pnas.172390999

Spectroscopic properties of aromatic dicarboximides. Part1.—N—H and N-methyl-substituted naphthalimides
journal, January 1994

  • Wintgens, Véronique; Valat, Pierre; Kossanyi, Jean
  • J. Chem. Soc., Faraday Trans., Vol. 90, Issue 3
  • DOI: 10.1039/FT9949000411

Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory
journal, July 2008

  • Rohrdanz, Mary A.; Herbert, John M.
  • The Journal of Chemical Physics, Vol. 129, Issue 3
  • DOI: 10.1063/1.2954017

Solvent Mediated Intramolecular Photoinduced Electron Transfer in a Fluorene-Perylene Bisimide Derivative
journal, November 2006

  • Neuteboom, Edda E.; Meskers, Stefan C. J.; Beckers, Edwin H. A.
  • The Journal of Physical Chemistry A, Vol. 110, Issue 45
  • DOI: 10.1021/jp061905n
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Enhancing the photoluminescence of surface anchored metal–organic frameworks: mixed linkers and efficient acceptors
    journal, January 2018

    • Oldenburg, M.; Turshatov, A.; Busko, D.
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 17
    • DOI: 10.1039/c7cp08452h

    Dynamic broadening alters triplet extinction coefficients in fluorene oligomers and polymers
    journal, January 2020

    • Cook, Andrew R.; Girimonti, Anthony; Sreearunothai, Paiboon
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5132798
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: