Publications

Anomalously high photocurrents in nanostructured electrodes : a new local microchip power source

Brinker, C.J.; Dunphy, Darren R.; Brozik, Susan M.; Brinker, C.J.

An increase in photocurrent has been observed at silicon electrodes coated with nanostructured porous silica films as compared to bare, unmodified silicon. Ultimately, to utilize this effect in devices such as sensors or microchip power supplies, the physical phenomena behind this observation need to be well characterized. To this end, Electrochemical Impedance Spectroscopy (EIS) was used to characterize the effect of surfactant-templated mesoporous silica films deposited onto silicon electrodes on the electrical properties of the electrode space-charge region in an aqueous electrolyte solution, as the electrical properties of this space-charge region are responsible for the photobehavior of semiconductor devices. A significant shift in apparent flat-band potential was observed for electrodes modified with the silica film when compared to bare electrodes; the reliability of this data is suspect, however, due to contributions from surface states to the overall capacitance of the system. To assist in the interpretation of this EIS data, a series of measurements at Pt electrodes was performed with the hope of decoupling electrode and film contributions from the EIS spectra. Surprisingly, the frequency-dependent impedance data for Pt electrodes coated with a surfactant-templated film was nearly identical to that observed for bare Pt electrodes, indicating that the mesoporous film had little effect on the transport of small electrolyte ions to the electrode surface. Pore-blocking agents (tetraalkylammonium salts) were not observed to inhibit this transport process. However, untemplated (non-porous) silica films dramatically increased film resistance, indicating that our EIS data for the Pt electrodes is reliable. Overall, our preliminary conclusion is that a shift in electrical properties in the space-charge region induced by the presence of a porous silica film is responsible for the increase in observed photocurrent.