A nonconjugated bridge in dimer-sensitized solar cells retards charge recombination without decreasing charge injection efficiency.

Dye sensitized solar cells (DSSCs) employing a dimer porphyrin, which was synthesised with two porphyrin units connected without conjugation, have shown that both porphyrin components can contribute to photocurrent generation, that is, more than 50 % internal quantum efficiency. In addition, the open-circuit voltage (Voc) of the DSSCs was higher than that of DSSCs using monomer porphyrins. In this paper, we first optimized cell structure and fabrication conditions. We obtained more than 80% incident photon to current conversion efficiency from the dimer porphyrin sensitized DSSCs and higher Voc and energy conversion efficiency than monomer porphyrin sensitized solar cells. To examine the origin of the higher Voc, we measured electron lifetime in the DSSCs with various conditions, and found that the dimer system increased the electron lifetime by improving the steric blocking effect of the dye layer, whilst the lack of a conjugated linker prevents an increase in the attractive force between conjugated sensitizers and the acceptor species in the electrolyte. The results support a hypothesis; dispersion force is one of the factors influencing the electron lifetime in DSSCs.

Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps.

Porphyrin molecules offer immense potential as the light harvesting component of dye-sensitised nanocrystalline TiO(2) solar cells. Synthetic porphyrin dyes were amongst the first dyes trialled for sensitisation of inorganic semiconducting oxides. Today, they exhibit the best performance reported for dye-sensitised solar cells. Accompanying the significant performance improvement over the last two decades is a much improved understanding of efficiency-determining fundamental electron transfer steps, from charge photogeneration to recombination. In this feature article we highlight our recent discoveries of the influence of porphyrin molecule structure on efficiency determining electron transfer kinetics and device performance by systematically changing the molecular structure and observing electron injection and recombination kinetics using time-resolved optical and electrical probes. Despite our observation of ultrafast charge injection for all porphyrin dyes studied by transient absorption spectroscopy, the injection yield estimated using an internal standard remains below 100% and depends strongly on the molecular structure. The observed discrepancy between kinetic competition and the injection yield is attributed to non-injecting dyes, probably arising due to inhomogeneity. A very interesting sub-ns (0.5 ns to 100 ns) charge recombination channel between photo-injected electrons and porphyrin cations is observed, which is found to be more prominent in free-base porphyrin dyes with a conjugated linker. Charge recombination between the acceptor species in the redox containing electrolyte and injected electrons is shown to be an important limitation of most porphyrin-sensitised solar cells, accelerated by the presence of porphyrin molecules at the TiO(2)-electrolyte interface. This recombination reaction is strongly dependent on the porphyrin molecular structure. Bulky substituents, using a porphyrin dimer instead of a porphyrin monomer, a light soaking treatment of freshly prepared films and co-sensitization of TiO(2) with multiple dyes are shown to be successful strategies to improve electron lifetime. Finally, new developments unique to porphyrin dye-sensitised solar cells, including performance enhancements from a light exposure treatment of a zinc porphyrin dye, a significant performance improvement observed after co-sensitisation of TiO(2) with free-base and zinc porphyrin dyes and the use of porphyrin dimers with increased light harvesting in thin-film TiO(2) solar cells are described.

Femtosecond diffuse reflectance transient absorption for dye-sensitized solar cells under operational conditions: effect of electrolyte on electron injection.

By applying diffuse reflectance transient absorption spectroscopy to dye-sensitized solar cells under operational conditions, we were able to directly correlate interfacial electron injection kinetics from a Ru complex sensitizer to a TiO(2) nanocrystalline electrode with the incident photon to current efficiency values. It was revealed that ionic liquid electrolytes reduced the initial electron injection efficiency by suppression of the approximately 100 ps process.

Zn-Zn porphyrin dimer-sensitized solar cells: toward 3-D light harvesting.

Zn-Zn porphyrin dimers have been incorporated into thin dye-sensitized solar cells (DSSCs) to boost their light harvesting efficiency. The photoexcited dimers show efficient and fast electron injection into TiO(2) indicating that both photoexcited chromophores contribute to current generation. The improved light harvesting ability coupled to enhanced DSSC performance demonstrates the potential of 3-D light harvesting arrays as next generation light harvesters for artificial solar energy conversion systems.

Interfacial electron-transfer kinetics in metal-free organic dye-sensitized solar cells: combined effects of molecular structure of dyes and electrolytes.

Electron diffusion coefficient, lifetime, and density in the TiO(2) electrode of dye-sensitized TiO(2) solar cells (DSCs) employing I(-)/I(3)(-) redox couples were measured with eight different metal-free organic dyes and three Ru complex dyes. At matched electron density, all DSCs using organic dyes (ODSCs) showed shorter electron lifetime with comparable or larger diffusion coefficients in comparison to the DSCs using the Ru dyes (RuDSC). The shorter lifetime was attributed partially to the slower dye cation reduction rate of the organic dyes by I(-), faster electron diffusion coefficient in the TiO(2), and mostly higher I(3)(-) concentration in the vicinity of the TiO(2) surface. Whereas a slight shift of the conduction band edge potential (E(cb)) of the TiO(2) was seen with a few organic dyes, no correlation was found with the dipole moment of the adsorbed dyes. This implies that the adsorbed dyes interact with cations in the electrolyte, so the direction of the dipole is altered or simply screened. The increase of [I(3)(-)] in the vicinity of the TiO(2) surface was interpreted with partial charge distribution of the dyes. Under one-sun conditions, less electron density due to shorter electron lifetime was found to be the main reason for the lower values of V(oc) for all ODSCs in comparison to that of RuDSCs. Among the organic dyes, having larger molecular size and alkyl chains showed longer electron lifetime, and thus higher V(oc). Toward higher open circuit voltage, a design guide of organic dyes controlling the electron lifetime is discussed.

The origin of open circuit voltage of porphyrin-sensitised TiO(2) solar cells.

Electron lifetime and diffusion coefficient measurements in highly efficient porphyrin-sensitised TiO(2) solar cells showed reduced electron lifetime, and consequently, lower photo-induced electron density under illumination compared to commonly used ruthenium dye (N719)-sensitised solar cells, which is proposed to be the origin of the generally lower open circuit voltage.