The iodide/triiodide redox shuttle has limited the efficiencies accessible in dye-sensitized solar cells. Here, we report mesoscopic solar cells that incorporate a Co^(II/III)tris(bipyridyl)–based redox electrolyte in conjunction with a custom synthesized donor-π-bridge-acceptor zinc porphyrin dye as sensitizer (designated YD2-o-C8). The specific molecular design of YD2-o-C8 greatly retards the rate of interfacial back electron transfer from the conduction band of the nanocrystalline titanium dioxide film to the oxidized cobalt mediator, which enables attainment of strikingly high photovoltages approaching 1 volt. Because the YD2-o-C8 porphyrin harvests sunlight across the visible spectrum, large photocurrents are generated. Cosensitization of YD2-o-C8 with another organic dye further enhances the performance of the device, leading to a measured power conversion efficiency of 12.3% under simulated air mass 1.5 global sunlight.

A series of porphyrin dyes with an electron-donating group (EDG) attached at a meso-position (YD1–YD8) have been designed and synthesized for use as sensitizers in dye-sensitized solar cells (DSSC). The nature of the EDG exerts a significant influence on the spectral, electrochemical and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins having an amino group show broadened Soret band and red-shifted Q bands with respect to those of reference porphyrin YD0. This phenomenon is more pronounced for porphyrins YD7 and YD8 that have a π-conjugated triphenylamine at the meso-position opposite the anchoring group. Upon introduction of an EDG at the meso-position, the potential for the first oxidation alters significantly to the negative whereas that for the first reduction changes inappreciably, indicating a decreased HOMO-LUMO gap. Results of density-functional theory (DFT) calculations support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino-substituted porphyrins YD1–YD4, which exhibit superior photovoltaic performance among all porphyrins under investigation. With long-chain alkyl groups on the diarylamino substituent, YD2 shows the best cell performance with J_SC = 13.4 mA cm⁻², V_OC = 0.71 V, and FF = 0.69, giving an overall efficiency 6.6% of power conversion under simulated one-sun AM1.5 illumination.

Novel porphyrin dyes YD14–YD17 with a push-pull framework were synthesized for dye-sensitized solar cells (DSSC); their spectral, electrochemical and photovoltaic properties were investigated. The absorption bands of these porphyrin dyes are broadened and red-shifted upon introduction of electron-donating groups (EDG) to the meso-positions via extension of π-conjugation. Electrochemical tests show that the first oxidation for these porphyrins occurs at a potential greater than that of the I⁻/I₃ ⁻ redox couple, and attachment of EDGs to the periphery of the porphyrin facilitates electron abstraction. The photovoltaic measurements show that YD14 and YD17 have a power conversion efficiency of ∼7%. Introduction of EDGs to various meso-positions is demonstrated to be achievable, and porphyrin dyes with appropriate EDGs are promising candidates for highly efficient DSSCs.