Influence of the TiCl4 treatment on nanocrystalline TiO2 films in dye-sensitized solar cells.: 2.: Charge density, band edge shifts, and quantification of recombination losses at short circuit

Chemical bath deposition of TiO2 from TiCl4 is an often used treatment that improves the photocurrent from dye-sensitized TiO2 solar cells. In this paper, charge density and kinetic data are used to show that the main effects of this treatment are an 80 mV downward shift in the TiO2 conduction band edge potential and a 20-fold decrease in the electron/electrolyte recombination rate constant. Together, these changes increase the quantum efficiency of charge separation at the interface, thus providing the observed increase in the photocurrent. The reduction in the recombination rate constant allows a greater concentration of electrons to accumulate at V,, thus offsetting the V,,c loss otherwise expected from the conduction band edge shift. Photocurrent transients and charge extraction data are used to show that the TiCl4 treatment has little effect on the transport of electrons at short circuit. The electron/electrolyte recombination rate constant at short circuit has been measured with the CCTPV (Constant Current Transient PhotoVoltage) technique. The results further confirm that any improvements in transport could not cause the beneficial effect of the TiCl4 treatment. Verification of the CCTPV technique is undertaken by comparison to transient absorption and by a model of the technique. Charge separation in dye-sensitized cells concerns two steps, charge injection and dye regeneration. Transient optical experiments to determine which process is improved by the TiCl4 treatment are discussed.