Access to Kinetic Constants via PMC Transients

The PMC transient-potential diagrams and the equations derived for PMC transients clearly show that bending of an energy band significantly influences the charge carrier lifetime in semiconductor/electrolyte junctions and that an accurate interpretation of the kinetic meaning of such transients is only possible when the band bending is known and controlled. 

Otherwise, the effect of electrode potential and kinetic parameters as contained in the relevant expression for the PMC signal (21), which controls the lifetime of PMC transients (40), may lead to an erroneous interpretation of kinetic mechanisms. The fact that lifetime measurements of PMC transients largely match the pattern of PMC-potential curves, showing peaks in accumulation and depletion of the semiconductor electrode and a minimum at the flatband potential [Figs. 13, 16-18, 34, and 36(b)], demonstrates that kinetic constants are accessible via PMC transient measurements, as indicated by the simplified relation (40) derived for the depletion layer of an n-type electrode. 

The fastest reliable PMC transients recorded at electrodes (ZnO single crystals24) were limited by the lifetime of a 10-ns laser flash. It was apparent from the nondeconvoluted signal at shorter time scales that much faster decay processes took place and would be accessible with faster laser pulses. 

Some precautions will be needed for successful measurements. The shorter the time scale the higher the photon densities that will be required. This leads to very high generation of excess charge carriers and to nonlinear phenomena of a complicated nature. 

How can such problems be counterbalanced Since a large capacitance of a semiconductor/electrolyte junction will not negatively affect the PMC transient measurement, a large area electrode (nanostructured materials) should be selected to decrease the effective excess charge carrier concentration (excess carriers per surface area) in the interface. PMC transient measurements have been performed at a sensitized nanostructured Ti02 liquidjunction solar cell.40 With a 10-ns laser pulse excitation, only the slow decay processes can be studied. The very fast rise time cannot be resolved, but this should be the aim of picosecond studies. Such experiments are being prepared in our laboratory, but using nanostructured 

---