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Integrating a Triplet-triplet Annihilation Up-conversion System to Enhance Dye-sensitized Solar Cell Response to Sub-bandgap Light
Published on: September 12, 2014
Enhancing the statistical probability factor in triplet-triplet annihilation photon upconversion via TIPS
Lukas Naimovičius1,2,3, Manvydas Dapkevičius2, Edvinas Radiunas2
1Institute of Materials Science of Barcelona (ICMAB-CSIC), Universitat Autònoma de Barcelona Bellaterra Barcelona 08193 Spain kasper.moth-poulsen@upc.edu pbharmoria@icmab.es.
Abstract:
We investigated the influence of triisopropylsilyl (TIPS) functionalization on annihilators in triplet-triplet annihilation photon upconversion, specifically focusing on their spin statistical probability factor. A new green-emitting annihilator 3,9-bis((triisopropylsilyl)ethynyl)perylene (TIPS-PY) displaying a record red-to-green TTA-UC quantum yield of 13.7% (50% theoretical maximum) was synthesized. This remarkable efficiency was achieved due to the following features of the TIPS functionalization of PY: (1) retaining a high fluorescence quantum yield of 95%, (2) reduced triplet energy to 1.29 eV enabling efficient triplet energy transfer (∼100%) from the sensitizer PdTPBP (T1 = 1.55 eV), and (3) a high efficiency of singlet generation after triplet coupling, indicated by the statistical probability factor, f = 39.2% ± 2.4%. Notably, the f value of TIPS-PY surpasses other annihilators in the 470-570 nm emission range. Excited state computational analysis using TheoDORE revealed a higher percentage of charge transfer character in S0S1 in TIPS-PY compared to PY, indicative of higher singlet-like character in their triplet-pair state 1(T1T1), which can enhance the coupling of the triplet-pair state with the excited singlet-state, thereby increasing the efficiency of singlet generation, a phenomenon undisclosed before. Furthermore, the suitable T1 of TIPS-PY enables upconversion of 730 nm light when sensitized with Os(m-peptpy)2(TFSI)2 (T1 = 1.63 eV), demonstrating the broad upconversion range of TIPS-PY in the phototherapeutic window desired for biological applications.
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