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Cited by 135Photochemistry and Electron Transfer StudiesOrganic Electronics and PhotovoltaicsLuminescence and Fluorescent Materials

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Switching between H- and J-type electronic coupling in single conjugated polymer aggregates

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Eder, Theresa, Stangl, Thomas, Gmelch, Max, Remmerssen, Klaas, Laux, Dirk, Höger, Sigurd, Lupton, John M., Vogelsang, Jan·2017·Nature Communications
DOI 10.1038/s41467-017-01773-0PMC PMC5696370
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Abstract

The aggregation of conjugated polymers and electronic coupling of chromophores play a central role in the fundamental understanding of light and charge generation processes. Here we report that the predominant coupling in isolated aggregates of conjugated polymers can be switched reversibly between H-type and J-type coupling by partially swelling and drying the aggregates. Aggregation is identified by shifts in photoluminescence energy, changes in vibronic peak ratio, and photoluminescence lifetime. This experiment unravels the internal electronic structure of the aggregate and highlights the importance of the drying process in the final spectroscopic properties. The electronic coupling after drying is tuned between H-type and J-type by changing the side chains of the conjugated polymer, but can also be entirely suppressed. The types of electronic coupling correlate with chain morphology, which is quantified by excitation polarization spectroscopy and the efficiency of interchromophoric energy transfer that is revealed by the degree of single-photon emission.

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Fig. 1 Switching and tuning between different types of electronic coupling. a Mechanisms of H-type and J-type coupling and the suppression of interactions and their expected relationship with aggregate morphology. b Switching between H-type and J-type coupling by drying (green box) and swelling (blue box) the aggregate embedded inside a polymer matrix by solvent vapor annealing. c Structures of samples used to tune between H-type (PPEB-1), J-type (PPEB-2), and suppressed coupling (PPEB-3) by changing the side chains
Fig. 1 Switching and tuning between different types of electronic coupling. a Mechanisms of H-type and J-type coupling and the suppression of interactions and their expected relationship with aggregate morphology. b Switching between H-type and J-type coupling by drying (green box) and swelling (blue box) the aggregate embedded inside a polymer matrix by solvent vapor annealing. c Structures of samples used to tune between H-type (PPEB-1), J-type (PPEB-2), and suppressed coupling (PPEB-3) by changing the side chainsCC BY · PubMed Central
Fig. 2 Switching between H-type and J-type coupling using solvent vapor annealing. a Schematic illustrating the splitting of single-spot PL with a dual-view unit into two detection channels, for photons with hv > 2.5 eV (denoted I green) and hv < 2.5 eV (denoted I red), and imaging onto different areas on the same CCD camera. The fraction of red emission for each single spot is defined as F red. b Accumulated wide-field dual-view fluorescence microscopy images of PPEB-1 aggregates of the same area from a 425 s movie during which the film conditions were changed. The first frame is accumulated during the first 50 s, the second frame at time 100–250 s and the last frame at 350–425 s. The z-scale is the same for all images. The first and the last frame are measured under ambient conditions and the central frame was obtained during SVA with a 1:4 ratio of toluene and hexane nitrogen vapor. Seven aggregates are marked with white circles. c Evolution of F red values with 500 ms time resolution from the seven aggregates (gray curves) and their average (red/orange curve). d, e Normalized PL spectra and transient PL decays of a single aggregate in a dry (red) and swollen state (orange). The PL decays are fitted by a single-exponential function with an offset to extract the PL lifetime. f Histograms of the full width at half maximum (FWHM) of the PL spectra of 89 swollen PPEB-1 aggregates (orange) and 131 PPEB-1 molecules (blue) (all individual spectra are shown in Supplementary Fig. 1)
Fig. 2 Switching between H-type and J-type coupling using solvent vapor annealing. a Schematic illustrating the splitting of single-spot PL with a dual-view unit into two detection channels, for photons with hv > 2.5 eV (denoted I green) and hv < 2.5 eV (denoted I red), and imaging onto different areas on the same CCD camera. The fraction of red emission for each single spot is defined as F red. b Accumulated wide-field dual-view fluorescence microscopy images of PPEB-1 aggregates of the same area from a 425 s movie during which the film conditions were changed. The first frame is accumulated during the first 50 s, the second frame at time 100–250 s and the last frame at 350–425 s. The z-scale is the same for all images. The first and the last frame are measured under ambient conditions and the central frame was obtained during SVA with a 1:4 ratio of toluene and hexane nitrogen vapor. Seven aggregates are marked with white circles. c Evolution of F red values with 500 ms time resolution from the seven aggregates (gray curves) and their average (red/orange curve). d, e Normalized PL spectra and transient PL decays of a single aggregate in a dry (red) and swollen state (orange). The PL decays are fitted by a single-exponential function with an offset to extract the PL lifetime. f Histograms of the full width at half maximum (FWHM) of the PL spectra of 89 swollen PPEB-1 aggregates (orange) and 131 PPEB-1 molecules (blue) (all individual spectra are shown in Supplementary Fig. 1)CC BY · PubMed Central
Fig. 3 Comparison of single-molecule and single-aggregate spectra. a–c Normalized single-molecule spectra plotted on a false-color intensity scale of PPEB-1 a, PPEB-2 b, and PPEB-3 c. d–f Single-aggregate spectra of PPEB-1 d, PPEB-2 e, and PPEB-3 f. Aggregates were grown by in situ SVA, subsequently dried under nitrogen and measured in air
Fig. 3 Comparison of single-molecule and single-aggregate spectra. a–c Normalized single-molecule spectra plotted on a false-color intensity scale of PPEB-1 a, PPEB-2 b, and PPEB-3 c. d–f Single-aggregate spectra of PPEB-1 d, PPEB-2 e, and PPEB-3 f. Aggregates were grown by in situ SVA, subsequently dried under nitrogen and measured in airCC BY · PubMed Central
Fig. 4 PL spectra and PL decays of single chains and single aggregates. Normalized PL spectra, transient PL decays, and spectral FWHM values extracted from the spectra in Fig. 3 and plotted in a histogram with 10 meV bin size for single molecules a–c and single aggregates d–f of PPEB-1 (red), PPEB-2 (orange), and PPEB-3 (green) in PMMA measured in air. Transient PL decays were fitted with an exponential plus an offset to account for the background, yielding the PL lifetimes stated in b and e
Fig. 4 PL spectra and PL decays of single chains and single aggregates. Normalized PL spectra, transient PL decays, and spectral FWHM values extracted from the spectra in Fig. 3 and plotted in a histogram with 10 meV bin size for single molecules a–c and single aggregates d–f of PPEB-1 (red), PPEB-2 (orange), and PPEB-3 (green) in PMMA measured in air. Transient PL decays were fitted with an exponential plus an offset to account for the background, yielding the PL lifetimes stated in b and eCC BY · PubMed Central
Fig. 5 Comparison of the statistics of single chains and aggregate samples. a–c Scatter plots of PL lifetime, τ PL, and PL intensity for single chains and isolated aggregates d–f formed by SVA of the three materials measured in air. The color encodes the fraction of red emission, F red, for each measured single particle, which ranges between 0.25 (blue) and 0.5 (red). Data from 391 a, 694 b, and 469 c single chains and 1196 d, 1881 e, and 889 f isolated aggregates are shown
Fig. 5 Comparison of the statistics of single chains and aggregate samples. a–c Scatter plots of PL lifetime, τ PL, and PL intensity for single chains and isolated aggregates d–f formed by SVA of the three materials measured in air. The color encodes the fraction of red emission, F red, for each measured single particle, which ranges between 0.25 (blue) and 0.5 (red). Data from 391 a, 694 b, and 469 c single chains and 1196 d, 1881 e, and 889 f isolated aggregates are shownCC BY · PubMed Central
Fig. 6 Morphology of single chains and isolated aggregates. a Sketch of the excitation polarization measurement technique and definition of the modulation depth, M. b M values for single chains and isolated aggregates c of the three samples measured in air. The spacing between the bars is varied for clarity and the histograms are normalized to the overall number of measurements (single chains: 1097, 1766, 977; aggregates: 743, 1062, 772) of spots yielding the probability of measuring a particular M value
Fig. 6 Morphology of single chains and isolated aggregates. a Sketch of the excitation polarization measurement technique and definition of the modulation depth, M. b M values for single chains and isolated aggregates c of the three samples measured in air. The spacing between the bars is varied for clarity and the histograms are normalized to the overall number of measurements (single chains: 1097, 1766, 977; aggregates: 743, 1062, 772) of spots yielding the probability of measuring a particular M valueCC BY · PubMed Central
Fig. 7 Photon statistics of single multichain aggregates measured in air. Accumulated second-order cross-correlation, g (2)(Δτ), curves for 57 PPEB-1 a, 47 PPEB-2 b, and 44 PPEB-3 c aggregates. The aggregates were excited by laser pulses (10 MHz repetition rate) to control the difference Δτ in photon arrival time between the two detectors. The antibunching dip at Δτ = 0 is apparent. In b, photon bunching occurs for ∣Δτ∣>0, which is described by a single-exponential fit (orange)
Fig. 7 Photon statistics of single multichain aggregates measured in air. Accumulated second-order cross-correlation, g (2)(Δτ), curves for 57 PPEB-1 a, 47 PPEB-2 b, and 44 PPEB-3 c aggregates. The aggregates were excited by laser pulses (10 MHz repetition rate) to control the difference Δτ in photon arrival time between the two detectors. The antibunching dip at Δτ = 0 is apparent. In b, photon bunching occurs for ∣Δτ∣>0, which is described by a single-exponential fit (orange)CC BY · PubMed Central

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Metadata

Authors
Eder, T., Stangl, T., Gmelch, M., Remmerssen, K., Laux, D., Höger, S., Lupton, J. M., & Vogelsang, J.
Affiliations
  • University of Regensburg (DE)
  • University of Bonn (DE)
Corresponding author
Vogelsang, Jan
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2017-11-21
Volume
8
Issue
1
Pages
1641-1641
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-017-01773-0
PMC
PMC5696370
OpenAlex
W2770794788
Cited by
135
References
72
Citations by year
2026: 9 · 2025: 10 · 2024: 17 · 2023: 14 · 2022: 21 · 2021: 21 · 2020: 22 · 2019: 10 · 2018: 11
FWCI
8.65
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • Europe PMC (PubMed Central) (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • University of Regensburg Publication Server (University of Regensburg) (acceptedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • University of Regensburg Publication Server (University of Regensburg)
Funders
  • Deutsche Forschungsgemeinschaft (GRK 1570)
  • Volkswagen Foundation
  • FP7 Ideas: European Research Council (305020)
Topics
  • Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Photochemistry and Electron Transfer Studies
  • Physical Sciences › Engineering › Electrical and Electronic Engineering › Organic Electronics and Photovoltaics
  • Physical Sciences › Materials Science › Materials Chemistry › Luminescence and Fluorescent Materials
Keywords
conjugated polymers, polymer aggregates, reversible switching, side-chain engineering, chain morphology, photoluminescence, vibronic coupling, single-photon emission

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