Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published February 29, 1996 | metadata_only
Journal Article

Theoretical and Experimental Upper Bounds on Interfacial Charge-Transfer Rate Constants between Semiconducting Solids and Outer-Sphere Redox Couples


Theoretical expressions for the charge-transfer rate constant at a semiconductor/liquid junction have been modified to include the effects of adiabaticity and the existence of a Helmholtz layer at the solid/liquid interface. These expressions have yielded an estimate of the maximum interfacial charge-transfer rate constant, at optimal exoergicity, for a semiconductor in contact with a random distribution of nonadsorbing, outer-sphere redox species. An experimental upper bound on this interfacial charge-transfer rate constant has been obtained through the determination of key energetic and kinetic properties for stable semiconductor electrodes in contact with outer-sphere redox species. For this purpose, n-Si/CH_3OH−dimethylferrocenium−dimethylferrocene, n-GaAs/CH_3CN−ferrocenium−ferrocene, and p-InP/CH_3CN−cobaltocenium−cobaltocene contacts were investigated using a combination of current density-potential and differential capacitance-potential methods. The upper limits for the interfacial charge-transfer rate constant at these semiconductor/liquid contacts were found to be consistent with the upper limits predicted by theory. The current density-potential behavior of n-InP and p-InP/Fe(CN)_6^(3-/4-)(aq) junctions was also examined in order to assess the validity of prior kinetic measurements on these interfaces.

Additional Information

© 1996 American Chemical Society. Received: June 27, 1995; In Final Form: November 8, 1995. We acknowledge the National Science Foundation (NSF), Grant CHE-9221311, for support of this work. K.E.P. also acknowledges the NSF for a predoctoral fellowship.

Additional details

August 20, 2023
August 20, 2023