Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers

Wenlin Zhang, Joel H. Bombile, Albree R. Weisen, Renxuan Xie, Ralph H. Colby, Michael John Janik, Scott Thomas Milner, Enrique Daniel Gomez

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

All conjugated polymers examined to date exhibit significant cumulative lattice disorder, although the origin of this disorder remains unclear. Using atomistic molecular dynamics (MD) simulations, the detailed structures for single crystals of a commonly studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) are obtained. It is shown that thermal fluctuations of thiophene rings lead to cumulative disorder of the lattice with an effective paracrystallinity of about 0.05 in the π–π stacking direction. The thermal-fluctuation-induced lattice disorder can in turn limit the apparent coherence length that can be observed in diffraction experiments. Calculating mobilities from simulated crystal structures demonstrates that thermal-fluctuation-induced lattice disorder even enhances charge transport in P3HT. The mean inter-chain charge transfer integral is enhanced with increasing cumulative lattice disorder, which in turn leads to pathways for fast charge transport through crystals.

Original languageEnglish (US)
Article number1900134
JournalMacromolecular Rapid Communications
Volume40
Issue number15
DOIs
StatePublished - Jan 1 2019

Fingerprint

Conjugated polymers
Charge transfer
Thiophenes
Thiophene
Crystal lattices
Molecular dynamics
Diffraction
Crystal structure
Single crystals
Crystals
Computer simulation
Hot Temperature
Experiments

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

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title = "Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers",
abstract = "All conjugated polymers examined to date exhibit significant cumulative lattice disorder, although the origin of this disorder remains unclear. Using atomistic molecular dynamics (MD) simulations, the detailed structures for single crystals of a commonly studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) are obtained. It is shown that thermal fluctuations of thiophene rings lead to cumulative disorder of the lattice with an effective paracrystallinity of about 0.05 in the π–π stacking direction. The thermal-fluctuation-induced lattice disorder can in turn limit the apparent coherence length that can be observed in diffraction experiments. Calculating mobilities from simulated crystal structures demonstrates that thermal-fluctuation-induced lattice disorder even enhances charge transport in P3HT. The mean inter-chain charge transfer integral is enhanced with increasing cumulative lattice disorder, which in turn leads to pathways for fast charge transport through crystals.",
author = "Wenlin Zhang and Bombile, {Joel H.} and Weisen, {Albree R.} and Renxuan Xie and Colby, {Ralph H.} and Janik, {Michael John} and Milner, {Scott Thomas} and Gomez, {Enrique Daniel}",
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Thermal Fluctuations Lead to Cumulative Disorder and Enhance Charge Transport in Conjugated Polymers. / Zhang, Wenlin; Bombile, Joel H.; Weisen, Albree R.; Xie, Renxuan; Colby, Ralph H.; Janik, Michael John; Milner, Scott Thomas; Gomez, Enrique Daniel.

In: Macromolecular Rapid Communications, Vol. 40, No. 15, 1900134, 01.01.2019.

Research output: Contribution to journalArticle

TY - JOUR

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AU - Zhang, Wenlin

AU - Bombile, Joel H.

AU - Weisen, Albree R.

AU - Xie, Renxuan

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AU - Janik, Michael John

AU - Milner, Scott Thomas

AU - Gomez, Enrique Daniel

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AB - All conjugated polymers examined to date exhibit significant cumulative lattice disorder, although the origin of this disorder remains unclear. Using atomistic molecular dynamics (MD) simulations, the detailed structures for single crystals of a commonly studied conjugated polymer, poly(3-hexylthiophene-2,5-diyl) (P3HT) are obtained. It is shown that thermal fluctuations of thiophene rings lead to cumulative disorder of the lattice with an effective paracrystallinity of about 0.05 in the π–π stacking direction. The thermal-fluctuation-induced lattice disorder can in turn limit the apparent coherence length that can be observed in diffraction experiments. Calculating mobilities from simulated crystal structures demonstrates that thermal-fluctuation-induced lattice disorder even enhances charge transport in P3HT. The mean inter-chain charge transfer integral is enhanced with increasing cumulative lattice disorder, which in turn leads to pathways for fast charge transport through crystals.

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