Proceedings of 6th International Conference on Hybrid and Organic Photovoltaics (HOPV14)
Publication date: 1st March 2014
Porphyrin-Sensitized Solar Cells (PSSCs) have attracted considerable interest exceeding the 12% of solar energy conversion efficiency.[1]The best-performing porphyrinic dyes appear to have push-pull architectures based on variously meso disubstituted ZnII-diarylporphyrinates, which require multistep synthetic pathways drastically reducing overall yields. A microwave-assisted synthetic procedure was developed, by some of us, to successfully obtain ß-substituted tetrarylporphyrinic dyes with good yields and in few reaction steps. Contrary to all expectations, these latter dyes provided similar or better conversion efficiencies in PSSCs[2]when compared to the push-pull meso disubstituted ZnII-diarylporphyrinic counterparts.
The kinetic fundamentals, which play the key role on interfacial charge separation and collection processes onto the TiO2 photoanode, were investigated by time-dependant spectroscopy and EIS analysis.[3]It was found that the unexpected better efficiency of the ß-substituted tetrarylporphyrinic dyes cannot be ascribed to a better injection process but rather to the more hindered macrocyclic core which promotes a superior passivation of the TiO2 surface against charge recombination with the oxidized specie (I3-) of the electrolyte. Moreover, the panchromatic effect on IPCE spectra of ZnII-porphyrinic dyes, when a dithienylethylene (DTE) system was introduced in ß position through different π-delocalized linkers, was also investigated.[4]Finally we also reported the differences in conversion efficiencies obtained when ß-substituted tetrarylporphyrinic dyes were wrapped by long alcoxy chains linked in various positions on the meso aryl rings.[5]
The present contribution summarizes the main results obtained by our research group in the field of PSSCs, with a particular attention on the better, and unexpected, conversion efficiencies recorded for ß-substituted ZnII-porphyrinates with respect to those of meso disubstituted homologues.
Schematic illustration of electron transfer processes on porpfhyrin-sensitized TiO2 photoanode
[1] Yella, A.; Lee, H.-W.; Tsao, H. N.; Yi, C.; Chandiran, A. K.; Nazeeruddin, M. K.; Diau, E. W.-G.; Yeh, C.-Y.; Zakeeruddin, S. M.; Grätzel, M., Porphyrin-Sensitized Solar Cells with Cobalt (II/III)–Based Redox Electrolyte Exceed 12 Percent Efficiency. Science 2011, 334 (6056), 629-634. [2] Di Carlo, G.; Orbelli Biroli, A.; Pizzotti, M.; Tessore, F.; Trifiletti, V.; Ruffo, R.; Abbotto, A.; Amat, A.; De Angelis, F.; Mussini, P. R., Tetraaryl ZnII Porphyrinates Substituted at β-Pyrrolic Positions as Sensitizers in Dye-Sensitized Solar Cells: A Comparison with meso-Disubstituted Push–Pull ZnII Porphyrinates. Chem. Eur. J. 2013, 19 (32), 10723-10740. [3] Di Carlo, G.; Caramori, S.; Trifiletti, V.; Pizzotti, M.; Orbelli Biroli, A.; Tessore, F.; Argazzi, R.; Bignozzi, C.A. paper in preparation. [4] Di Carlo, G.; Orbelli Biroli, A.; Tessore, F.; Pizzotti, M.; Mussini, P. R.; Amat, A.; De Angelis, F.; Abbotto, A.; Trifiletti, V.; Ruffo, R., Physicochemical Investigation of the Panchromatic Effect on β-Substituted ZnII Porphyrinates for DSSCs: The Role of the π Bridge between a Dithienylethylene Unit and the Porphyrinic Ring. J. Phys. Chem. C 2014. [5] Orbelli Biroli, A.; Tessore, F.; Vece, V.; Di Carlo, G.; Mussini, P. R.; Trifiletti, V.; De Marco, L.; Pizzotti, M. paper in preparation.
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