Suppression of luminescence quenching at the nanometer scale in Gd_2O_3 doped with Eu~(3+) or Tb~(3+): Systematic comparison between nanometric and macroscopic samples of life-time, quantum yield, radiative and non-radiative decay rates

摘要

By systematically studying the evolution of the optical properties with the content of some doping elements (Eu and Tb) in cubic gadolinium oxide, we demonstrated that the luminescence quenching could be almost entirely suppressed by elaboration of the samples in the nanometer range. Indeed, even if the proportion of quenchers (here surface hydroxyl groups) does increase at this scale, each rare-earth cation possesses an electronic configuration that depends on its distance from the surface and then slightly differs from that of the surrounding atoms. This difference almost eliminates any resonant transfer of excitation between all the atoms within the particle and suppresses a significant proportion of non-radiative losses. As a consequence, the quantum yield is not affected by the phenomenon of luminescence quenching because of concentration that is usually encountered in macroscopic samples. The emission can then be increased by a factor of about 3 for Tb and 5 for Eu simply by increasing the doping content. Moreover, the lifetime is significantly increased compared to macroscopic samples and, contrary to what happens at the macroscopic scale, does not depend on the doping content. This result opens new strategies to increase the emission of many fluorophores already commercialized, provided that the bcc structure is effectively preserved in the desired application.