Concentration Quenching in Upconversion Nanocrystals

Abstract

Despite considerable effort to improve upconversion (UC) in lanthanide-doped nanocrystals (NCs), the maximum reported efficiencies remain below 10%. Recently, we reported on low Er³⁺- and Yb³⁺-doped NaYF₄ NCs giving insight into fundamental processes involved in quenching for isolated ions. In practice, high dopant concentrations are required and there is a trend toward bright UC in highly doped NCs. Here, additional quenching processes due to energy transfer and migration add to a reduction in UC efficiency. However, a fundamental understanding on how concentration quenching affects the quantum efficiency is lacking. Here, we report a systematic investigation on concentration-dependent decay dynamics for Er³⁺ or Yb³⁺ doped at various concentrations (1-100%) in core and core-shell NaYF₄ NCs. The qualitative and quantitative analyses of luminescence decay curves and emission spectra show strong concentration quenching for the green-emitting Er^{3+ 4}S_3/2 and NIR-emitting ⁴I_11/2 levels, whereas concentration quenching for the red-emitting ⁴F_9/2 level and the IR-emitting ⁴I_13/2 level is limited. The NIR emission of Yb³⁺ remains efficient even at concentration as high as 60% Yb³⁺, especially in core-shell NCs. Finally, the role of solvent quenching was investigated and reveals a much stronger quenching in aqueous media that can be explained by the high-energy O-H vibrations. The present study uncovers a more complete picture of quenching processes in highly doped UC NCs and serves to identify methods to further optimize the efficiency by careful tuning of lanthanide concentrations and core-shell design.