Efficiency Considerations for SnO2-Based Dye-Sensitized Solar Cells.

A comparative study of mesoporous thin films based on SnO2 (rutile) and TiO2 (anatase) nanocrystallites sensitized to visible light with [Ru(dtb)2(dcb)](PF6)2, where dtb = 4,4'-(tert-butyl)2-2,2'-bipyridine and dcb = 4,4'-(CO2H)2-2,2'-bipyridine, in CH3CN electrolyte solutions is reported to identify the reason(s) for the low efficiency of SnO2-based dye-sensitized solar cells (DSSCs). Pulsed laser excitation resulted in rapid excited state injection (kinj > 108 s-1) followed by sensitizer regeneration through iodide oxidation to yield an interfacial charge separated state abbreviated as MO2(e-)|Ru + I3-. Spectral features associated with I3- and the injected electron MO2(e-) were observed as well as a hypsochromic shift of the metal-to-ligand charge-transfer absorption of the sensitizer attributed to an electric field. The field magnitude ranged from 0.008 to 0.39 MV/cm and was dependent on the electrolyte cation (Mg2+ or Li+) as well as the oxide material. Average MO2(e-) + I3- → recombination rate constants quantified spectroscopically were about 25 times smaller for SnO2 (6.0 ± 0.14 s-1) than for TiO2 (160 ± 10 s-1). Transient photovoltage measurements of operational DSSCs indicated a 78 ms lifetime for electrons injected into SnO2 compared to 27 ms for TiO2; behavior that is at odds with the view that recombination with I3- underlies the low efficiencies of nanocrystalline SnO2-based DSSCs. In contrast, the average rate constant for charge recombination with the oxidized sensitizer, MO2(e-)|-S+ → MO2|-S, was about 2 orders of magnitude larger for SnO2 (k = 9.8 × 104 s-1) than for TiO2 (k = 1.6 × 103 s-1). Sensitizer regeneration through iodide oxidation were similar for both oxide materials (kreg = 6 ± 1 × 1010 M-1 s-1). The data indicate that enhanced efficiency from SnO2-based DSSCs can be achieved by identifying alternative redox mediators that enable rapid sensitizer regeneration and by inhibiting recombination of the injected electron with the oxidized sensitizer.

Electric Fields Control TiO2(e(-)) + I3(-) → Charge Recombination in Dye-Sensitized Solar Cells.

The electric fields generated by excited-state electron injection into anatase TiO2 nanocrystallites are screened by cations present in the external electrolyte. With some assumptions, a newly discovered electroabsorption signature enables quantification of the electric field strength experienced by surface-anchored dye molecules. Here, it was found that the fields increased in the order Na(+) < Li(+) < Mg(2+) < Ca(2+), with magnitudes of 1.1 MV/cm for Na(+) and 2.2 MV/cm for Ca(2+), values that were insensitive to whether the anion was iodide or perchlorate. The magnitude of the field was directly related to average TiO2(e(-)) + I3(-) → charge recombination rate constants abstracted from time-resolved kinetic data. Extrapolation to zero field provided an estimate of recombination dynamics when diffusion alone controlled I3(-) mass transport, k = 300 s(-1). The decreased rate constants measured after excited-state injection were attributed to migration of I3(-) away from the TiO2. Cation transference coefficients were tabulated that ranged from t = 0.97 for Ca(2+) to 0.40 for Na(+) and represented the ability of the unscreened electric field to block the TiO2(e(-)) + I3(-) → charge recombination reaction. This data provides the first compelling evidence that the anionic nature of I3(-) inhibits unwanted charge recombination in dye-sensitized solar cells.