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

Title: Side chain dynamics in semiconducting polymer MEH-PPV

Abstract

We report that the characteristic nanoscale dynamics of the alkyl side groups in the light-emitting polymer poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] have been investigated using quasi-elastic neutron scattering (QENS). The measurements were taken below the polymer's glass transition (T ≤ Tg ≃ 353 K), where the main backbone is in a rigid state and does not contribute to the broadening of the QENS signal. An analytical diffusion model consisting of a static term and two dynamical components, characterizing the flexible side groups, provide an excellent fit to the experimental data. The two observed dynamical processes are all localized in character, with no meaningful dependence on temperature. The faster process, with characteristic timescale of ~18 ps at room temperature (RT), can be linked to the average mobility of the terminal protons of the alkyl chain, while the slower process, with characteristic timescale of ~170 ps at RT, to those protons at the other end of the alkyl chain, closest to the backbone. Lastlyl, while the fraction of mobile protons contributing to the QENS signal increases with increasing temperature, the characteristic timescale and confining volume within which the protons are able to move locally depend chiefly on the polymer conformational state.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1488691
Alternate Identifier(s):
OSTI ID: 1485521
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Applied Polymer Science
Additional Journal Information:
Journal Volume: 136; Journal Issue: 0; Journal ID: ISSN 0021-8995
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; optical and photovoltaic applications; polymer dynamics; quasi‐elastic neutron scattering; semi‐conducting polymer; spectroscopy

Citation Formats

Osti, Naresh C., Mamontov, Eugene, Daemen, Luke L., Browning, Jim, Keum, Jong K., Ho, Hoi Chun, Chen, Jihua, Hong, Kunlun, and Omar Diallo, Souleymane. Side chain dynamics in semiconducting polymer MEH-PPV. United States: N. p., 2018. Web. doi:10.1002/APP.47394.
Osti, Naresh C., Mamontov, Eugene, Daemen, Luke L., Browning, Jim, Keum, Jong K., Ho, Hoi Chun, Chen, Jihua, Hong, Kunlun, & Omar Diallo, Souleymane. Side chain dynamics in semiconducting polymer MEH-PPV. United States. doi:10.1002/APP.47394.
Osti, Naresh C., Mamontov, Eugene, Daemen, Luke L., Browning, Jim, Keum, Jong K., Ho, Hoi Chun, Chen, Jihua, Hong, Kunlun, and Omar Diallo, Souleymane. Wed . "Side chain dynamics in semiconducting polymer MEH-PPV". United States. doi:10.1002/APP.47394. https://www.osti.gov/servlets/purl/1488691.
@article{osti_1488691,
title = {Side chain dynamics in semiconducting polymer MEH-PPV},
author = {Osti, Naresh C. and Mamontov, Eugene and Daemen, Luke L. and Browning, Jim and Keum, Jong K. and Ho, Hoi Chun and Chen, Jihua and Hong, Kunlun and Omar Diallo, Souleymane},
abstractNote = {We report that the characteristic nanoscale dynamics of the alkyl side groups in the light-emitting polymer poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] have been investigated using quasi-elastic neutron scattering (QENS). The measurements were taken below the polymer's glass transition (T ≤ Tg ≃ 353 K), where the main backbone is in a rigid state and does not contribute to the broadening of the QENS signal. An analytical diffusion model consisting of a static term and two dynamical components, characterizing the flexible side groups, provide an excellent fit to the experimental data. The two observed dynamical processes are all localized in character, with no meaningful dependence on temperature. The faster process, with characteristic timescale of ~18 ps at room temperature (RT), can be linked to the average mobility of the terminal protons of the alkyl chain, while the slower process, with characteristic timescale of ~170 ps at RT, to those protons at the other end of the alkyl chain, closest to the backbone. Lastlyl, while the fraction of mobile protons contributing to the QENS signal increases with increasing temperature, the characteristic timescale and confining volume within which the protons are able to move locally depend chiefly on the polymer conformational state.},
doi = {10.1002/APP.47394},
journal = {Journal of Applied Polymer Science},
number = 0,
volume = 136,
place = {United States},
year = {2018},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Chemistry of Conducting Polythiophenes
journal, January 1998


Single Molecule Spectroscopy of Conjugated Polymer Chains in an Electric Field-Aligned Liquid Crystal
journal, January 2008

  • Chang, Wei-Shun; Link, Stephan; Yethiraj, Arun
  • The Journal of Physical Chemistry B, Vol. 112, Issue 2
  • DOI: 10.1021/jp076345m

Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments
journal, November 2014

  • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
  • DOI: 10.1016/j.nima.2014.07.029

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

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Relaxation dynamics and exciton energy transfer in the low-temperature phase of MEH-PPV
journal, June 2015

  • Consani, Cristina; Koch, Federico; Panzer, Fabian
  • The Journal of Chemical Physics, Vol. 142, Issue 21
  • DOI: 10.1063/1.4918645

Relating the physical structure and optical properties of conjugated polymers using neutron reflectivity in combination with photoluminescence spectroscopy
journal, March 2004

  • Mitchell, William J.; Burn, Paul L.; Thomas, Robert K.
  • Journal of Applied Physics, Vol. 95, Issue 5
  • DOI: 10.1063/1.1644636

Temperature dependence of molecular dynamics and supramolecular aggregation in MEH-PPV films: A solid-state NMR, X-ray and fluorescence spectroscopy study
journal, December 2008


The Impact of Polymer Regioregularity on Charge Transport and Efficiency of P3HT:PCBM Photovoltaic Devices
journal, May 2010

  • Mauer, Ralf; Kastler, Marcel; Laquai, Frédéric
  • Advanced Functional Materials, Vol. 20, Issue 13
  • DOI: 10.1002/adfm.201000320

Structure and Dynamics of Conjugated Polymers in Liquid Crystalline Solvents
journal, May 2007


Effect of Polymorphism, Regioregularity and Paracrystallinity on Charge Transport in Poly(3-hexylthiophene) [P3HT] Nanofibers
journal, November 2013

  • Poelking, Carl; Andrienko, Denis
  • Macromolecules, Vol. 46, Issue 22
  • DOI: 10.1021/ma4015966

Local Dynamics of Syndiotactic Poly(methyl methacrylate) Using Molecular Dynamics Simulation
journal, December 2006

  • Chen, Chunxia; Maranas, Janna K.; García-Sakai, Victoria
  • Macromolecules, Vol. 39, Issue 26
  • DOI: 10.1021/ma0610562

Persistent photoconductivity in poly( p -phenylenevinylene): Spectral response and slow relaxation
journal, June 1993


Resolution of VISION, a crystal-analyzer spectrometer
journal, June 2009

  • Seeger, Philip A.; Daemen, Luke L.; Larese, John Z.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 604, Issue 3
  • DOI: 10.1016/j.nima.2009.03.204

Quasielastic neutron scattering in soft matter
journal, December 2009

  • Sakai, Victoria García; Arbe, Arantxa
  • Current Opinion in Colloid & Interface Science, Vol. 14, Issue 6
  • DOI: 10.1016/j.cocis.2009.04.002

Effect of antimicrobial peptide on the dynamics of phosphocholine membrane: role of cholesterol and physical state of bilayer
journal, January 2015

  • Sharma, V. K.; Mamontov, E.; Anunciado, D. B.
  • Soft Matter, Vol. 11, Issue 34
  • DOI: 10.1039/C5SM01562F

Recent progress on polymer dynamics by neutron scattering: From simple polymers to complex materials
journal, October 2012

  • Colmenero, Juan; Arbe, Arantxa
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 2
  • DOI: 10.1002/polb.23178

Photoluminescence and Relaxation Processes in MEH−PPV
journal, February 2005

  • Cossiello, R. F.; Kowalski, E.; Rodrigues, P. C.
  • Macromolecules, Vol. 38, Issue 3
  • DOI: 10.1021/ma048340i

The Impact of Polymer Dynamics on Photoinduced Carrier Formation in Films of Semiconducting Polymers
journal, November 2015

  • Ogata, Yudai; Kawaguchi, Daisuke; Tanaka, Keiji
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
  • DOI: 10.1021/acs.jpclett.5b02255

Alkyl Chain Dynamics in Monolayer-Protected Clusters (MPCs):  A Quasielastic Neutron-Scattering Investigation
journal, April 2002

  • Mitra, S.; Nair, Binoj; Pradeep, T.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 15
  • DOI: 10.1021/jp0144146

Quasi-elastic neutron scattering study of the molecular motions of methanol adsorbed on H-ZSM-5
journal, March 1986

  • Jobic, H.; Renouprez, A.; Bee, M.
  • The Journal of Physical Chemistry, Vol. 90, Issue 6
  • DOI: 10.1021/j100278a020

Water dynamics in rigid ionomer networks
journal, December 2016

  • Osti, N. C.; Etampawala, T. N.; Shrestha, U. M.
  • The Journal of Chemical Physics, Vol. 145, Issue 22
  • DOI: 10.1063/1.4971209

Mesoscale Morphology and Charge Transport in Colloidal Networks of Poly(3-hexylthiophene)
journal, May 2011

  • Newbloom, Gregory M.; Kim, Felix S.; Jenekhe, Samson A.
  • Macromolecules, Vol. 44, Issue 10, p. 3801-3809
  • DOI: 10.1021/ma2000515

Microstructure of thin films of photoluminescent semiconducting polymers
journal, January 1998


Intermediate motions as studied by solid-state separated local field NMR experiments
journal, March 2008

  • deAzevedo, Eduardo Ribeiro; Saalwachter, Kay; Pascui, Ovidiu
  • The Journal of Chemical Physics, Vol. 128, Issue 10
  • DOI: 10.1063/1.2831798

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


Momentum and energy dependent resolution function of the ARCS neutron chopper spectrometer at high momentum transfer: Comparing simulation and experiment
journal, November 2016

  • Diallo, S. O.; Lin, J. Y. Y.; Abernathy, D. L.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 835
  • DOI: 10.1016/j.nima.2016.08.027

Molar Mass Dependence of Polyethylene Chain Dynamics. A Quasi-Elastic Neutron Scattering Investigation
journal, December 2012

  • Arrighi, V.; Tanchawanich, J.; Telling, Mark T. F.
  • Macromolecules, Vol. 46, Issue 1
  • DOI: 10.1021/ma301922j

Inelastic-neutron-scattering studies of poly( p -phenylene vinylene)
journal, December 1994


Dynamics in Protein Powders on the Nanosecond–Picosecond Time Scale Are Dominated by Localized Motions
journal, September 2013

  • Nickels, Jonathan D.; García Sakai, Victoria; Sokolov, Alexei P.
  • The Journal of Physical Chemistry B, Vol. 117, Issue 39
  • DOI: 10.1021/jp4058884

Solid-state nuclear magnetic resonance study of relaxation processes in MEH-PPV
journal, May 2005


Disorder controlled hole transport in MEH-PPV
journal, February 2004


Neutron scattering study of the picosecond dynamics of polybutadiene and polyisoprene
journal, July 1995


Luminescent phosphonium polyelectrolyte prepared from a diphosphine chromophore: synthesis, photophysics, and layer-by-layer assembly
journal, January 2010

  • Tennyson, Eleanor G.; He, Susan; Osti, Naresh C.
  • Journal of Materials Chemistry, Vol. 20, Issue 37
  • DOI: 10.1039/c0jm01430c

Bipyridyl-modified phosphonium polyelectrolytes: synthesis, photophysics, metal ion coordination and layer-by-layer assembly with anionic conjugated polymers
journal, January 2013

  • Kristufek, Samantha L.; Maltais, Thora R.; Tennyson, Eleanor G.
  • Polymer Chemistry, Vol. 4, Issue 21
  • DOI: 10.1039/c3py20765j

Modeling the Dynamics of Chromophores in Conjugated Polymers: The Case of Poly(2-methoxy-5-(2′-ethylhexyl)oxy 1,4-phenylene vinylene) (MEH-PPV)
journal, February 2009

  • De Leener, Caroline; Hennebicq, Emmanuelle; Sancho-Garcia, Juan-Carlos
  • The Journal of Physical Chemistry B, Vol. 113, Issue 5
  • DOI: 10.1021/jp8029902

An Order–Disorder Transition in the Conjugated Polymer MEH-PPV
journal, July 2012

  • Köhler, Anna; Hoffmann, Sebastian T.; Bässler, Heinz
  • Journal of the American Chemical Society, Vol. 134, Issue 28
  • DOI: 10.1021/ja302408a

Effect of Polymer Nanoparticle Formation on the Efficiency of Polythiophene Based “Bulk-Heterojunction” Solar Cells
journal, August 2008

  • Moulé, Adam J.; Allard, Sybille; Kronenberg, Nils M.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 33
  • DOI: 10.1021/jp8043016

Use of Picosecond Fluorescence Dynamics as an Indicator of Exciton Motion in Conjugated Polymers:  Dependence on Chemical Structure and Temperature
journal, December 2001

  • Bjorklund, Thomas G.; Lim, Sang-Hyun; Bardeen, Christopher J.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 48
  • DOI: 10.1021/jp0124746

A time-of-flight backscattering spectrometer at the Spallation Neutron Source, BASIS
journal, August 2011

  • Mamontov, E.; Herwig, K. W.
  • Review of Scientific Instruments, Vol. 82, Issue 8
  • DOI: 10.1063/1.3626214

Structure and morphology control in thin films of regioregular poly(3-hexylthiophene)
journal, July 2011

  • Brinkmann, Martin
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 49, Issue 17
  • DOI: 10.1002/polb.22310

Space-Dependent Dynamics in 1,4-Polybutadiene Nanocomposite
journal, August 2013

  • Roh, J. H.; Tyagi, M.; Hogan, T. E.
  • Macromolecules, Vol. 46, Issue 16
  • DOI: 10.1021/ma401597r

Structure and Dynamics of Hyperbranched Polymer/Layered Silicate Nanocomposites
journal, March 2013

  • Fotiadou, S.; Karageorgaki, C.; Chrissopoulou, K.
  • Macromolecules, Vol. 46, Issue 7
  • DOI: 10.1021/ma302405q