Structure-Dependent Accessibility of Phonon-Coupled Radiative Relaxation Pathways Probed by X-ray-Excited Optical Luminescence. Academic Article uri icon

abstract

  • Rare-earth scheelites represent a diverse family of compounds with multiple degrees of freedom, which enables the incorporation of a wide range of lanthanide color centers. Precise positioning of quantum objects is attainable by the choice of alkali cations and lattice connectivity of polyanion units. Herein, we report the structure-dependent energy transfer and lattice coupling of optical transitions in La3+- and Dy3+-containing scheelite-type double and quadruple molybdates NaLa1-xDyx(MoO4)2 and Na5La1-xDyx(MoO4)4. X-ray excitation of La3+ core states generates excited-state electron-hole pairs, which, upon thermalizing across interconnected REO8 polyhedra in double molybdates, activate a phonon-coupled excited state of Dy3+. A pronounced luminescence band is observed corresponding to optical cooling of the lattice upon preferential radiative relaxation from a "hot" state. In contrast, combined X-ray absorption near-edge structure and X-ray-excited optical luminescence studies reveal that such a lattice coupling mechanism is inaccessible in quadruple molybdates with a greater separation of La3+-Dy3+ centers.

published proceedings

  • J Phys Chem Lett

author list (cited authors)

  • Udayakantha, M., Perera, S. S., Davidson, R. D., Zuin, L., Rabuffetti, F. A., & Banerjee, S.

publication date

  • January 1, 2021 11:11 AM