Molecular Engineering of Zinc-Porphyrin Sensitisers for p-Type Dye-Sensitised Solar Cells.

Design of novel efficient light-harvesters for p-type dye-sensitised solar cells (DSSCs) is indispensable for further advances in this photovoltaic technology. Herein, a novel D-π-A (D=donor, π=π-conjugated linker, A=acceptor) sensitiser, ZnP1, featuring an electron acceptor, perylenemonoimide (PMI), connected to an electron donor, di(p-carboxyphenyl)amine (DCPA), through fluorene and a zinc(II) porphyrin with alkyl chains as a π-conjugated bridge is introduced. Spectroscopic and electrochemical characterisation of this dye along with a newly synthesised PMI-free reference dye ZnP0 has been undertaken to demonstrate strong electron coupling between the DCPA donor and PMI acceptor subunits through the porphyrin ring in ZnP1, which redshifts the light absorption onset to the near-IR region. When integrated into p-DSSCs based on a mesoporous nickel(II) oxide semiconductor electrode and a tris(acetylacetonato) iron(III/II) redox mediator, ZnP1 exhibits an onset of the incident photon-to-current conversion efficiency at 800 nm and a power conversion efficiency of up to 0.92 % under simulated 100 mW cm-2 AM 1.5 G irradiation. This is the highest efficiency of the porphyrin-based p-DSSCs hitherto reported.