Light Activated Electrochemistry: Light Intensity and pH Dependence on Electrochemical Performance of Anthraquinone Derivatized Silicon

We seek to understand how the thermodynamics and kinetics of anthraquinone-containing self-assembled monolayer on silicon electrodes are affected by two key experimental variables: the intensity of the light assisting the anthraquinone/anthrahydroquinone redox process and the local solution environment. The substrates are chemically passivated poorly doped p-type silicon electrodes. The study presents a strategy for the selective modulation of either the anodic or the cathodic process occurring at the interface. Cyclic voltammetry studies showed that unlike for a proton-coupled electron transfer process performed at metallic electrodes, for the redox reaction of the anthraquinone unit on a silicon electrode it becomes possible to (i) selectively facilitate only the oxidation process by increasing the electrolyte pH or (ii) at a given pH value to increase the illumination intensity to anodically shift the onset of the reduction step only but leave the oxidation process thermodynamic unchanged. A model concerning the proton coupled electron transfer mechanism was proposed, where the electron transfer is the rate-determining step for the anthraquinone reduction while a deprotonation step is the rate-determining event for the anthrahydroquinone oxidation on poorly doped illuminated p-type silicon

The rapid formation of functional monolayers on silicon under mild conditions

We report on an exceedingly mild chemical functionalization of hydrogen-terminated Si(100) with unactivated and unprotected bifunctional α,ω-dialkynes. Monolayer formation occurs rapidly in the dark, and at room temperature, from dilute solutions of an aromatic-conjugated acetylene. The method addresses the poor reactivity of p-type substrates under mild conditions. We suggest the importance of several factors, including an optimal orientation for electron transfer between the adsorbate and the Si surface, conjugation of the acetylenic function with a π-system, as well as the choice of a solvent system that favors electron transfer and screens Coulombic interactions between surface holes and electrons. The passivated Si(100) electrode is amenable to further functionalization and shown to be a viable model system for redox studies at non-oxide semiconductor electrodes in aqueous solutions

The rapid formation of functional monolayers on silicon under mild conditions

We report on an exceedingly mild chemical functionalization of hydrogen-terminated Si(100) with unactivated and unprotected bifunctional α,ω-dialkynes. Monolayer formation occurs rapidly in the dark, and at room temperature, from dilute solutions of an aromatic-conjugated acetylene. The method addresses the poor reactivity of p-type substrates under mild conditions. We suggest the importance of several factors, including an optimal orientation for electron transfer between the adsorbate and the Si surface, conjugation of the acetylenic function with a π-system, as well as the choice of a solvent system that favors electron transfer and screens Coulombic interactions between surface holes and electrons. The passivated Si(100) electrode is amenable to further functionalization and shown to be a viable model system for redox studies at non-oxide semiconductor electrodes in aqueous solutions