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- Gillett, Alexander J., et al.
(författare)
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Spontaneous exciton dissociation enables spin state interconversion in delayed fluorescence organic semiconductors
- 2021
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Ingår i: Nature Communications. - : Nature Portfolio. - 2041-1723. ; 12:1
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Tidskriftsartikel (refereegranskat)abstract
- Engineering a low singlet-triplet energy gap (Delta E-ST) 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 x 10(5) cm(-1)) and a relatively large Delta E-ST of 0.2 eV. In isolated BF2 molecules, intramolecular rISC is slow (delayed lifetime = 260 mu s), 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 similar to 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 Delta E-ST in organic DF emitters.
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| 2. |
- Gillett, Alexander J., et al.
(författare)
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The role of charge recombination to triplet excitons in organic solar cells
- 2021
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Ingår i: Nature. - : NATURE PORTFOLIO. - 0028-0836 .- 1476-4687. ; 597:7878, s. 666-
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Tidskriftsartikel (refereegranskat)abstract
- The use of non-fullerene acceptors (NFAs) in organic solar cells has led to power conversion efficiencies as high as 18%(1). However, organic solar cells are still less efficient than inorganic solar cells, which typically have power conversion efficiencies of more than 20%(2). A key reason for this difference is that organic solar cells have low open-circuit voltages relative to their optical bandgaps(3), owing to non-radiative recombination(4). For organic solar cells to compete with inorganic solar cells in terms of efficiency, non-radiative loss pathways must be identified and suppressed. Here we show that in most organic solar cells that use NFAs, the majority of charge recombination under open-circuit conditions proceeds via the formation of non-emissive NFA triplet excitons; in the benchmark PM6:Y6 blend(5), this fraction reaches 90%, reducing the open-circuit voltage by 60 mV. We prevent recombination via this non-radiative channel by engineering substantial hybridization between the NFA triplet excitons and the spin-triplet charge-transfer excitons. Modelling suggests that the rate of back charge transfer from spin-triplet charge-transfer excitons to molecular triplet excitons may be reduced by an order of magnitude, enabling re-dissociation of the spin-triplet charge-transfer exciton. We demonstrate NFA systems in which the formation of triplet excitons is suppressed. This work thus provides a design pathway for organic solar cells with power conversion efficiencies of 20% or more. A substantial pathway for energy loss in organic solar cells may be suppressed by engineering hybridization between non-fullerene acceptor triplet excitons and spin-triplet charge transfer excitons.
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