Photocurrent enhancement by multilayered porphyrin sensitizers in a photoelectrochemical cell.

Multilayer Zn(II) tetraphenylporphyrin chromophores, assembled using copper-catalyzed azide-alkyne cycloaddition (CuAAC), provide a new sensitization scheme that could be useful in dye-sensitized solar cells (DSSCs). We report on the photoelectrochemical responses of multilayer films of Zn(II) 5,10,15,20-tetra(4-ethynylphenyl)porphyrin (1) assembled on planar ITO substrates operating as a p-type DSSC using three different redox mediators. The traditional I(-)/I3(-) redox couple results in the greatest short circuit current densities (JSC) but very low open circuit potentials (VOC). The use of cobalt sepulchrate ([Co(sep)](2+/3+)) and cobalt tris-bipyridine ([Co(bpy)3](2+/3+)) as redox mediators generates higher VOC values, but at the expense of lower photocurrents. These results highlight the inherent differences in the interactions between the redox mediator and Zn(II) tetraphenylporphyrin multilayer films. Increasing the porphyrin content through multilayer growth proved to be effective in increasing the performance of photoelectrochemical cells with all three redox mediators. Cells using I(-)/I3(-) reached maximum performance (power output) at five porphyrin layers, [Co(bpy)3](2+/3+) at five layers, and [Co(sep)](2+/3+) at three layers. For all mediators, JSC increases with the addition of porphyrin layers beyond a monolayer. However, JSC reaches a maximum value at a point greater than one layer after which it decreases, presumably due to exciton diffusion limitations and the insulating effects of the multilayer film. Similarly, all cells also reach a maximum VOC beyond one porphyrin layer. We show that porphyrin arrays assembled using newly developed CuAAC layer-by-layer growth may be useful as a multilayer sensitization scheme for use in photoelectrochemical cells.