Role of Disorder in the Extent of Interchain Delocalization and Polaron Generation in Polythiophene Crystalline Domains

Kyu Hyung Park, Sung Yun Son, Jun Oh Kim, Gyeongho Kang, Taiho Park, Dongho Kim

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

To understand how disorder within conjugated polymer aggregates influences the polaron generation process, we investigated poly(3-hexylthiophene) (P3HT) and a congeneric random copolymer incorporating 33 mol % substituent-free thiophene units (RP33). Steady-state absorption and fluorescence spectra showed that increasing the intrachain torsional disorder in aggregates increases the energy and breadth of the density of states (DOS). By extracting polaron dynamics in the transient absorption spectra, we found that an activation energy barrier of 0.05 eV is imposed on the charge separation process in P3HT, whereas that in RP33 is essentially barrierless. We also found that a significant amount of excitons in P3HT are deactivated by traps, while no trapped excitons are generated in RP33. This efficient polaron generation in RP33 was attributed to the excess energy and enhanced interchain delocalization of precursor states provided by the intrachain torsional disorder and the close-packing structure in the absence of hexyl substituents.

Original languageEnglish
Pages (from-to)3173-3180
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume9
Issue number12
DOIs
Publication statusPublished - 2018 Jun 21

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Gene Conversion
Excitons
disorders
Crystalline materials
Energy barriers
Conjugated polymers
Thiophene
Polymers
excitons
absorption spectra
Absorption spectra
Thiophenes
Copolymers
Activation energy
Fluorescence
polarization (charge separation)
thiophenes
copolymers
traps
activation energy

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physical and Theoretical Chemistry

Cite this

Park, Kyu Hyung ; Son, Sung Yun ; Kim, Jun Oh ; Kang, Gyeongho ; Park, Taiho ; Kim, Dongho. / Role of Disorder in the Extent of Interchain Delocalization and Polaron Generation in Polythiophene Crystalline Domains. In: Journal of Physical Chemistry Letters. 2018 ; Vol. 9, No. 12. pp. 3173-3180.
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Role of Disorder in the Extent of Interchain Delocalization and Polaron Generation in Polythiophene Crystalline Domains. / Park, Kyu Hyung; Son, Sung Yun; Kim, Jun Oh; Kang, Gyeongho; Park, Taiho; Kim, Dongho.

In: Journal of Physical Chemistry Letters, Vol. 9, No. 12, 21.06.2018, p. 3173-3180.

Research output: Contribution to journalArticle

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AU - Park, Kyu Hyung

AU - Son, Sung Yun

AU - Kim, Jun Oh

AU - Kang, Gyeongho

AU - Park, Taiho

AU - Kim, Dongho

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AB - To understand how disorder within conjugated polymer aggregates influences the polaron generation process, we investigated poly(3-hexylthiophene) (P3HT) and a congeneric random copolymer incorporating 33 mol % substituent-free thiophene units (RP33). Steady-state absorption and fluorescence spectra showed that increasing the intrachain torsional disorder in aggregates increases the energy and breadth of the density of states (DOS). By extracting polaron dynamics in the transient absorption spectra, we found that an activation energy barrier of 0.05 eV is imposed on the charge separation process in P3HT, whereas that in RP33 is essentially barrierless. We also found that a significant amount of excitons in P3HT are deactivated by traps, while no trapped excitons are generated in RP33. This efficient polaron generation in RP33 was attributed to the excess energy and enhanced interchain delocalization of precursor states provided by the intrachain torsional disorder and the close-packing structure in the absence of hexyl substituents.

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