Surface plasmon coupled chemiluminescence during adsorption of oxygen on magnesium surfaces

The dissociative adsorption of oxygen molecules on magnesium surfaces represents a non-adiabatic reaction exhibiting exoelectron emission, chemicurrent generation, and weak chemiluminescence. Using thin film Mg/Ag/p-Si(111) Schottky diodes with 1 nm Mg on a 10-60 nm thick Ag layer as 2π-photodetectors, the chemiluminescence is internally detected with a much larger efficiency than external methods. The chemically induced photoyield shows a maximum for a Ag film thickness of 45 nm. The enhancement is explained by surface plasmon coupled chemiluminescence, i.e., surface plasmon polaritons are effectively excited in the Ag layer by the oxidation reaction and decay radiatively leading to the observed photocurrent. Model calculations of the maximum absorption in attenuated total reflection geometry support the interpretation. The study demonstrates the extreme sensitivity and the practical usage of internal detection schemes for investigating surface chemiluminescence.