Multitype Electronic Interactions in Precursor Solutions of Molecular Doped P3HT Polymer
Spin-casting of molecularly doped polymer solution mixtures is one of the commonly used methods to obtain conductive organic semiconductor films. In spin-casted films, electronic interaction between the dopant and polymer is one of the crucial factors that dictates the doping efficiency. Here, we investigate excitonic couplings using ultrafast two-dimensional electronic spectroscopy to examine the different types of electronic interactions in ion pairs of the prototype F4TCNQ-doped P3HT polymer system in a precursor solution mixture for spin-casting. Off-diagonal peaks in the 2D spectra clearly establish the excitonic coupling between P3HT+ and F4TCNQ- ions in solution. The observed excitonic coupling is the direct manifestation of a Coulombic interaction between the ion pair. The excited-state lifetime of F4TCNQ- in ion pairs shows biexponential decay at 30 and 200 fs, which hints toward the presence of a heterogeneous population with different interaction strengths. To examine the nature of these different types of interactions in solution mixtures, we study the system using molecular dynamics simulations on a fully solvated model employing the generalized Amber force field. We retrieve three dominant interaction modes of F4TCNQ anions with P3HT: side chain, π-stack, and slipped stack. To quantify these interactions, we complement our studies with electronic structure calculations, which reveal the excitonic coupling strengths of ∼ 75 cm-1 for side chain, ∼ 150 cm-1 for π-π-stack, and ∼69 cm-1 for slipped stack. These various interaction modes provide information about the key geometries of the seed structures in precursor solution mixtures, which may determine the final structures in spin-casted films. The insights gained from our study may guide new strategies to control and ultimately tune Coulomb interactions in polymer-dopant solutions.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:128 |
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| Enthalten in: |
The journal of physical chemistry. B - 128(2024), 13 vom: 04. Apr., Seite 3249-3257 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Tiwari, Vandana [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 04.04.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.jpcb.4c00584 |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM369971582 |
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| 520 | |a Spin-casting of molecularly doped polymer solution mixtures is one of the commonly used methods to obtain conductive organic semiconductor films. In spin-casted films, electronic interaction between the dopant and polymer is one of the crucial factors that dictates the doping efficiency. Here, we investigate excitonic couplings using ultrafast two-dimensional electronic spectroscopy to examine the different types of electronic interactions in ion pairs of the prototype F4TCNQ-doped P3HT polymer system in a precursor solution mixture for spin-casting. Off-diagonal peaks in the 2D spectra clearly establish the excitonic coupling between P3HT+ and F4TCNQ- ions in solution. The observed excitonic coupling is the direct manifestation of a Coulombic interaction between the ion pair. The excited-state lifetime of F4TCNQ- in ion pairs shows biexponential decay at 30 and 200 fs, which hints toward the presence of a heterogeneous population with different interaction strengths. To examine the nature of these different types of interactions in solution mixtures, we study the system using molecular dynamics simulations on a fully solvated model employing the generalized Amber force field. We retrieve three dominant interaction modes of F4TCNQ anions with P3HT: side chain, π-stack, and slipped stack. To quantify these interactions, we complement our studies with electronic structure calculations, which reveal the excitonic coupling strengths of ∼ 75 cm-1 for side chain, ∼ 150 cm-1 for π-π-stack, and ∼69 cm-1 for slipped stack. These various interaction modes provide information about the key geometries of the seed structures in precursor solution mixtures, which may determine the final structures in spin-casted films. The insights gained from our study may guide new strategies to control and ultimately tune Coulomb interactions in polymer-dopant solutions | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Li, Xin |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Zheng |e verfasserin |4 aut | |
| 700 | 1 | |a Jacobs, Ian E |e verfasserin |4 aut | |
| 700 | 1 | |a Duan, Hong-Guang |e verfasserin |4 aut | |
| 700 | 1 | |a Sirringhaus, Henning |e verfasserin |4 aut | |
| 700 | 1 | |a Miller, R J Dwayne |e verfasserin |4 aut | |
| 700 | 1 | |a Jha, Ajay |e verfasserin |4 aut | |
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