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When redox active molecules are covalently tethered to the surface of then-doped silicon, light induces their oxidation by the semiconductor. Tovisualize this charge separation we have followed the formation and decay ofthe surface photovoltage by an auxiliary transparent electrode, which serves asa capacitive probe that picks up the transient surface photovoltage. Thismethod has been used in electronics and biophysics but is novel for the surfaceredox chemistry. The probe provides both the direction of the charge transferand the resolution of the dynamics. Its application is independent of theoptical properties of the semiconductor. Laser initiation of the reactionpermits quantitative measurements of the reactions with the rate constants~108-103 s-1. The electron injection from covalently tethered NTCI(A) moleculesinto silicon was fast (k >109 s-1). The back electron transfer is poly-dispersewith the components ranging from ~10 microseconds and up.

Time-Resolved Measurements of the Interfacial Charge Transfers by Capacitive Voltage Probe