Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors
Unson, Darcy M. L.
Conaghan, Patrick J.
Nature Publishing Group UK
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Gillett, A. J., Tonnelé, C., Londi, G., Ricci, G., Catherin, M., Unson, D. M. L., Casanova, D., et al. (2021). Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors. Nature Communications, 12 (1) https://doi.org/10.1038/s41467-021-26689-8
Abstract: Engineering a low singlet-triplet energy gap (ΔEST) is necessary for efficient reverse intersystem crossing (rISC) in delayed fluorescence (DF) organic semiconductors but results in a small radiative rate that limits performance in LEDs. Here, we study a model DF material, BF2, that exhibits a strong optical absorption (absorption coefficient = 3.8 × 105 cm−1) and a relatively large ΔEST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 μs), but in aggregated films, BF2 generates intermolecular charge transfer (inter-CT) states on picosecond timescales. In contrast to the microsecond intramolecular rISC that is promoted by spin-orbit interactions in most isolated DF molecules, photoluminescence-detected magnetic resonance shows that these inter-CT states undergo rISC mediated by hyperfine interactions on a ~24 ns timescale and have an average electron-hole separation of ≥1.5 nm. Transfer back to the emissive singlet exciton then enables efficient DF and LED operation. Thus, access to these inter-CT states, which is possible even at low BF2 doping concentrations of 4 wt%, resolves the conflicting requirements of fast radiative emission and low ΔEST in organic DF emitters.
Article, /639/301/1019/1020/1091, /639/624/1020/1091, /132, /140/125, /120, article
Is supplemented by: https://doi.org/10.17863/CAM.76085
EC | EU Framework Programme for Research and Innovation H2020 | H2020 Priority Excellent Science | H2020 European Research Council (H2020 Excellent Science - European Research Council) (670405)
RCUK | Engineering and Physical Sciences Research Council (EPSRC) (EP/M01083X/1, EP/M005143/1)
Simons Foundation (601946)
External DOI: https://doi.org/10.1038/s41467-021-26689-8
This record's URL: https://www.repository.cam.ac.uk/handle/1810/330864