Enhancing upconversion luminescence of highly doped lanthanide nanoparticles through phase transition delay

Abstract

Doping of rare earth (RE) ions in a low-phonon-energy host matrix is an effective strategy to enhance the upconversion luminescence (UCL) of lanthanide-doped nanoparticles. However, doping of optically inactive RE ions at high concentrations can cause an undesirable phase transition of the host matrix, with concomitant decrease in luminescence. Herein, we present a phase-transition-delay protocol to effectively preserve the pure orthorhombic phase of a KLu2F7:Yb3+,Er3+ system, even at high RE dopant concentrations. The proposed concept can be realized by incorporating a set of optically inactive RE dopants, i.e., Y3+ or Gd3+, with different ionic radii to replace the Lu3+ ions in the host matrix to overcome the energy barrier of the phase transition. The nanoparticles were synthesized in a high-boiling solvent or at a high reaction temperature. We observed maximal UCL of Er3+ at different Y3+ or Gd3+ dopant concentrations; the optimal Y3+ or Gd3+ concentration at which maximal UCL is observed is 10 mol% for samples prepared by a water-based hydrothermal route, while it is 30 mol% for samples prepared by an oleic acid-based hydrothermal route. Further, this optimal concentration could be increased to as much as 50 mol% by adopting a high reaction temperature. The high doping of Y3+ or Gd3+ can efficiently lead to enhanced upconversion performance of the final materials (as much as 32-fold and 9-fold enhancements in the upconversion intensity and quantum yield, respectively, are achieved). The UCL enhancement is caused by the break-down of the symmetry of lanthanide sites in the crystal lattice induced by Y3+ or Gd3+, which enhances the energy transfer probabilities between Yb3+ and Er3+. Our findings highlight a convenient route to simultaneously tune the phase transition of the host and upconversion output, and this strategy can be applied to other upconversion host materials.