Photochemistry on Thin Metal Films: Probe of Electron Dynamics in Metal-Semiconductor Heterosystems

The surface photochemistry of NO2 on ultrathin epitaxial Ag films on Si(100) substrates has been studied with the goal to employ it as a tool to unravel the electron dynamics in such films. An increase of the photodesorption cross section is observed--a factor of 5 for 266 nm light and 12 nm film thickness--when the film thickness is decreased, despite the fact that the optical absorbtivity decreases. The increased photodesorption cross section is interpreted to result from photon absorption in the Si substrate producing electrons at energies and parallel momenta which are not allowed in Ag. These electrons penetrate through the Ag film despite the gap in the surface projected band structure utilizing quantum resonances