BEHAVIOR OF SI PHOTOELECTRODES UNDER HIGH LEVEL INJECTION CONDITIONS. 1. STEADY-STATE CURRENT-VOLTAGE PROPERTIES AND QUASI-FERMI LEVEL POSITIONS UNDER ILLUMINATION

The behavior of the quasi-Fermi levels of electrons and holes at various semiconductor/liquid interfaces has been probed through the use of thin, high purity, low dopant density single crystal Si photoelectrodes. Since standard Air Mass 1.5 illumination is sufficient to produce high level injection conditions in such samples, minimal electric fields can be present near the solid/liquid interface. Under these conditions, efficient charge separation relies on establishment of kinetic asymmetries at the back contacts while effectively sustaining photogenerated carrier concentration gradients in the photoelectrode. These conditions were achieved for Si/CH3OH interfaces in contact with the 1,1‘-dimethylferrocene+/0, cobaltocene+/0, methyl viologen2+/+, and decamethylferrocene+/0 redox couples. For redox couples having energies near the top of the Si valence band, such as 1,1‘-dimethylferrocene+/0, the sample acted like an n-type photoelectrode, yielding large photovoltages for collection of electrons at the ba...