Diketopyrrolopyrrole (DPP) is one of the most common building blocks for small molecules and conjugated polymers designed for organic electronic applications. By attaining a detailed understanding of the photophysical behaviour for a simple DPP-based molecule in fullerene blends, we establish a foundation for spectroscopic investigations into more complex DPP-based systems.
Transient absorption spectroscopy (TAS) and time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy are used to examine bulk heterojunction blend films of a small diketopyrrolopyrrole-based molecule, 2,5-bis(2-hexyldecyl)-3,6-di(thiophen-2-yl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione (TDPP) with the common fullerene derivatives [6,6]-phenyl-C61-butyric acid methyl ester (PC60BM) and [6,6]-phenyl-C71-butyric acid methyl ester (PC70BM).
Following pulsed laser excitation, the spectral signatures of a fullerene anion and a TDPP triplet state are observed on the picosecond timescale by TAS. The presence of these species imply the formation of a TDPP:PCBM charge transfer state that subsequently undergoes ultra-fast spin-mixing and geminate recombination to produce a TDPP triplet state. The overall photophysical mechanism is confirmed by TR-EPR spectroscopy, which unambiguously shows that the TDPP triplet is formed via spin-mixing in the TDPP:PCBM charge transfer state, rather than direct intersystem crossing from the excited singlet state.
Salvadori, E., Luke, N., Shaikh, J., Leventis, A., Bronstein, H., Kay, C. and Clarke, T., 2017. Ultra-fast spin-mixing in a diketopyrrolopyrrole monomer/fullerene blend charge transfer state. Journal of Materials Chemistry A.
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