Effects of Core-modification on Porphyrin Sensitizers to the Efficiencies of Dye-sensitized Solar Cells

To study dye-sensitized solar cells (DSSCs) with core-modified porphyrins as the sensitizing dyes, three porphyrins with an ethynyl benzoic acid as an anchoring group are prepared. The properties of free-base regular porphyrin (N4), thiaporphyrin (N3S) and oxaporphyrin (N3O) were thoroughly studied by spectroscopic methods, DFT calculations, and photovoltaic measurements. Replacing one of the porphyrinic core nitrogen atoms by oxygen or sulfur considerably changes the absorption spectra. The Soret band of the N3O and N3S observed bathochromic shifts of 3-9 nm while the Q band reaches 700 nm to the near-infrared region. The overall conversion efficiencies of the DSSCs based on these porphyrins are in the order N4 (3.66%) >> N3S (0.22%) > N3O (0.01%). The time-correlated single photon counting observed short fluorescence lifetimes for N3O adsorbed both on TiO2 and Al2O3 which explicates the poor efficiency of DSSC using N3O as the photosensitizer.