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Research Article | Open Access

Yb- and Er concentration dependence of the upconversion luminescence of highly doped NaYF4:Yb,Er/NaYF4:Lu core/shell nanocrystals prepared by a water-free synthesis

Christian Würth1, Bettina Grauel1, Monika Pons1, Florian Frenzel1, Philipp Rissiek2, Kerstin Rücker1, Markus Haase1(), Ute Resch-Genger1 ()
Federal Institute for Materials Research and Testing (BAM), Division Biophotonics, Richard-Willstaetter-Str. 11, 12489 Berlin, Germany
Institut für Chemie Neuer Materialien, Fachbereich Biologie/Chemie, Universität Osnabrück, Barbarastraße 7, 49076 Osnabrück, Germany
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Absolute upconversion luminescence (UCL) measurements of highly doped NaYF4:Yb,Er/NaYF4:Lu core/shell nanocrystals prepared by an elaborate water-free synthesis reveal that high Yb3+ concentrations of up to 98% barely reduce the record quantum yield of ~9% for an Er3+ concentration of 2% and present a very effective tool to boost particle brightness. Increasing the Er3+ concentration to 40% leads to a 7-fold decrease in UCL for heavily Yb3+-doped nanocrystals, yet this reduction in UCL can be compensated by high excitation power densities.

Abstract

High sensitizer and activator concentrations have been increasingly examined to improve the performance of multi-color emissive upconversion (UC) nanocrystals (UCNC) like NaYF4:Yb,Er and first strategies were reported to reduce concentration quenching in highly doped UCNC. UC luminescence (UCL) is, however, controlled not only by dopant concentration, yet by an interplay of different parameters including size, crystal and shell quality, and excitation power density (P). Thus, identifying optimum dopant concentrations requires systematic studies of UCNC designed to minimize additional quenching pathways and quantitative spectroscopy. Here, we quantify the dopant concentration dependence of the UCL quantum yield (ΦUC) of solid NaYF4:Yb,Er/NaYF4:Lu upconversion core/shell nanocrystals of varying Yb3+ and Er3+ concentrations (Yb3+ series: 20%‒98% Yb3+; 2% Er3+; Er3+ series: 60% Yb3+; 2%‒40% Er3+). To circumvent other luminescence quenching processes, an elaborate synthesis yielding OH-free UCNC with record ΦUC of ~ 9% and ~ 25 nm core particles with a thick surface shell were used. High Yb3+ concentrations barely reduce ΦUC from ~ 9% (20% Yb3+) to ~ 7% (98% Yb3+) for an Er3+ concentration of 2%, thereby allowing to strongly increase the particle absorption cross section and UCNC brightness. Although an increased Er3+ concentration reduces ΦUC from ~ 7 % (2% Er3+) to 1% (40%) for 60% Yb3+. Nevertheless, at very high P (> 1 MW/cm2) used for microscopic studies, highly Er3+-doped UCNC display a high brightness because of reduced saturation. These findings underline the importance of synthesis control and will pave the road to many fundamental studies of UC materials.

Keywords

highly doped upconversion nanocrystalscore/shell nanoparticlesupconversion luminescence efficiencyNaYF4:YbErconcentration quenching

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Nano Research
Volume 15 Issue 10,
October 2022
Pages 9639-9646
DOI: 10.1007/s12274-022-4570-5
Cite this article:
Würth C, Grauel B, Pons M, et al. Yb- and Er concentration dependence of the upconversion luminescence of highly doped NaYF4:Yb,Er/NaYF4:Lu core/shell nanocrystals prepared by a water-free synthesis. Nano Research, 2022, 15(10): 9639-9646. https://doi.org/10.1007/s12274-022-4570-5
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