Photoelectrochemical characterisation and optimisation of electrodeposited ZnO thin films sensitised by porphyrins and phthalocyanines.

Hybrid thin films of crystalline ZnO modified by 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrinato zinc (TSTPPZn) and 2,9,16,23-tetrasulfophthalocyaninatozinc(II) (TSPcZn) were prepared by electrochemical deposition from aqueous zinc salt solutions. A "one-step" process with the sensitisers adsorbed during ZnO deposition represented the most simple approach. ZnO was also grown independently in the presence of Eosin Y as a structure-directing agent, which was then removed and the sensitisers were chemisorbed from solutions ("readsorption" method). The photoelectrochemical characteristics of the electrodes were studied by photocurrent spectra and by time-resolved photocurrent measurements in an acetonitrile-based solution containing I3(-)/I(-) as the redox electrolyte. In films with both sensitisers present, both sensitisers worked in parallel providing panchromatic sensitisation. Recombination of electrons injected into the conduction band of ZnO with remaining holes in the HOMO of the sensitisers was indicated for the one-step films, but was considerably suppressed for the films prepared by the readsorption method. Films prepared by the readsorption method showed a significantly increased efficiency by an increased surface area and suppressed recombination.