Molecular spectroscopy of dye aggregates by scanning-tunneling-microscope-induced light emission

A bromide-modified silver (111) surface, covered by Jelly-type aggregates of a cyanine dye, is investigated by scanning tunneling microscopy (STM) in air. We show that, under appropriate conditions, light is emitted out of the junction by inelastic electron tunneling. Study of the relation between the light intensity and the tunnel bias clearly reveals a molecular influence on the light emission. Furthermore, through a spectral analysis, we show that sharp resonances appear for dye-covered surfaces by coupling of tip-induced plasmons with molecular excitations. This demonstrates that through STM-induced luminescence local spectroscopic information can be obtained on molecules.