Plasmonic Enhancement or Energy Transfer? On the Luminescence of Gold-, Silver-, and Lanthanide-Doped Silicate Glasses and Its Potential for Light-Emitting Devices

With the technique of synchrotron X-ray activation, molecule-like non-plasmonic gold and silver particles in soda-lime silicate glass can be generated. The luminescence energy transfer between these species and lanthanide(III) ions is studied. As a result, a significant lanthanide luminescence enhancement by a factor of up to 250 under non-resonant UV excitation is observed. The absence of a distinct gold and silver plasmon resonance absorption, respectively, the missing nanoparticle signals in previous SAXS and TEM experiments, the unaltered luminescence lifetime of the lanthanide ions compared to the non-enhanced case, and an excitation maximum at 300-350 nm (equivalent to the absorption range of small noble metal particles) indicate unambiguously that the observed enhancement is due to a classical energy transfer between small noble metal particles and lanthanide ions, and not to a plasmonic field enhancement effect. It is proposed that very small, molecule-like noble metal particles (such as dimers, trimers, and tetramers) first absorb the excitation light, undergo a singlet-triplet intersystem crossing, and finally transfer the energy to an excited multiplet state of adjacent lanthanide(III) ions. X-ray lithographic microstructuring and excitation with a commercial UV LED show the potential of the activated glass samples as bright light-emitting devices with tunable emission colors.