Photoelectrochemical properties of alternating multilayer films composed of titania nanosheets and Zn porphyrin

Alternating multilayer films composed of titania nanosheets and Zn porphyrins were prepared by use of a previously reported Langmuir-Blodgett film-transfer method in order to fabricate photoelectrochemical devices. Closely packed titania nanosheet monolayers on indium tin oxide (ITO), mica, and quartz surfaces strongly adsorbed cationic 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrinatozinc]4+ (ZnTMPyP4+) by electrostatic interactions. The alternating deposition process afforded nanometer-scale multilayer films with the following structure: solid surface/(titania nanosheet/ZnTMPyP4+)n (n is the number of layers). The multilayer films were characterized by various physical measurements, including AFM, XRD, and UV-visible spectra. The visible-light irradiation of this multilayer film on an ITO electrode in the presence of triethanolamine as an electron donor yielded an anodic photocurrent. The action spectrum was consistent with the absorption spectrum of ZnTMPyP4+, which indicates that the photoexcitation of ZnTMPyP4+ is responsible for the photocurrent generation. However, the photocurrent density decreased with an increasing number of layers, which indicates that the harvesting of photoexcited electrons vertically through the titania nanosheets in the ITO/(titania nanosheet/ZnTMPyP4+)n structure was not efficient. To overcome this problem, the use of a lateral interlayer connection to all of the titania nanosheets with Ag paste was examined. As a result, a dramatic improvement in the photocurrent density was obtained. Thus, for efficient photocurrent generation with the titania nanosheet-ZnTMPyP4+ composite material, the lateral connection to all of the titania nanosheet layers is effective.