Because solar energy is the most abundant renewable energy resource, the clear connection between human activity and global warming has strengthened the interest in photovoltaic science. Dye-sensitized solar cells (DSSCs) provide a promising low-cost technology for harnessing this energy source. Until recently, much of the research surrounding DSSCs had been focused on the sensitization of n-type semiconductors, such as titanium dioxide (Gratzel cells). In an n-type dye-sensitized solar cell (n-DSSC), an electron is injected into the conduction band of an n-type semiconductor (n-SC) from the excited state of the sensitizer. Comparatively few studies have examined the sensitization of wide bandgap p-type semiconductors. In a p-type DSSC (p-DSSC), the photoexcited sensitizer is reductively quenched by hole injection into the valence band of a p-type semiconductor (p-SC). The study of p-DSSCs is important both to understand the factors that control the rate of hole photoinjection and to aid the rational design of efficient p-DSSCs. In theory, p-DSSCs should be able to work as efficiently as n-DSSCs. In addition, this research provides a method for preparing tandem DSSCs consisting of a TiO(2)-photosensitized anode and a photosensitized p-type SC as a cathode. Tandem DSSCs are particularly important because they represent low-cost photovoltaic devices whose photoconversion efficiencies could exceed 15%. This Account describes recent research results on p-DSSCs. Because these photoelectrochemical devices are the mirror images of conventional n-DSSCs, they share some structural similarities, but they use different materials and have different charge transfer kinetics. In this technology, nickel oxide is the predominant p-SC material used, but much higher photoconversion efficiencies could be achieved with new p-SCs materials with deeper valence band potential. Currently, iodide/triiodide is the main redox mediator of electron transport within these devices, but we expect that this material could be advantageously replaced with more efficient redox couples. We also discuss valuable information obtained by ultrafast transient absorption spectroscopy, which sheds some light on the factors that govern the efficiency of the cell. Notably, we demonstrate that ultrafast hole injection generally occurs between the sensitizer and the SC, but the resulting charge-separated state (e.g. electron on the sensitizer and hole in the VB) is short-lived and recombines quickly. So far, the only effective strategy for slowing the back recombination reaction relies on a bimolecular system consisting of the sensitizer linked to an electron acceptor, which increases the separation distance between the charges. A photoconversion efficiency of 0.41% under AM 1.5 was recently measured with a p-type DSSC using this strategy.

In tandem: Employing a molecular dyad and a cobalt-based electrolyte gives a threefold-increase in open-circuit voltage (V(OC)) for a p-type NiO device (V(OC) = 0.35 V), and a fourfold better energy conversion efficiency. Incorporating these improvements in a TiO(2)/NiO tandem dye-sensitized solar cell (TDSC), results in a TDSC with a V(OC) = 0.91 V (see figure; CB = conductance band, VB = valence band).