Enhanced red up-conversion of β-NaYF4:Er3+,Tm3+ microcrystals for bio-imaging applications

Abstract

Pure red fluorescence generated by near infrared (NIR) excitation is desired for bio-imaging with high biological penetration, but without cell damage or multi-photon photo-toxicity. In this work, β-NaYF4:Er3+ and β-NaYF4:Er3+,Tm3+ microcrystals were synthesized using a novel hydrothermal method. β-NaYF4:Er3+ microcrystals exhibited intense green and red up-conversion emissions under 976 nm laser diode excitation. The introduction of Tm3+ ions into β-NaYF4:Er3+ resulted in strong inhibition of green up-conversion emission (Er3+:2H11/2 /4S3/2→4I15/2) and, consequently, red up-conversion emission (Er3+:4F9/2→4I15/2) was significantly promoted. To simultaneously restrain green up-conversion emissions and enhance red up-conversion emissions, the optimal concentrations of Er3+ and Tm3+ ions were determined to be 20 mol% and 2.0 mol%, respectively. The red/green up-conversion emission intensity ratio increased from ~1.80 (β-NaYF4:20Er3+, mol%) to ~78 (β-NaYF4:20Er3+,2Tm3+, mol%) after the addition of 2 mol% Tm3+ ions to β-NaYF4:20Er3+ (mol%). The red up-conversion emission intensity of β-NaYF4:20Er3+,2Tm3+ was stronger than that for commercial red up-conversion phosphors (NaYF4 and ZnF2) under the same experimental conditions. Based on the results of the emission spectra, luminescence rise, and decay profiles, the mechanism of enhanced red up-conversion emission by Tm3+ ion co-doping in β-NaYF4:20Er3+,2Tm3+ (mol%) was proposed. The bio-fluorescence experiment under NIR excitation proves that β-NaYF4:Er3+,Tm3+ microcrystals have potential applications in bio-imaging.