Colloidal synthesis and blue based multicolor upconversion emissions of size and composition controlled monodisperse hexagonal NaYF4 : Yb,Tmnanocrystals

Abstract

Monodisperse β-NaYF₄ : Yb,Tm nanocrystals with controlled size (25–150 nm), shape (sphere, hexagonal prism, and hexagonal plate), and composition (Yb: 20–40%, Tm: 0.2–5%) were synthesized from the thermolysis of metal trifluoroacetates in hot surfactant solutions. The upconversion (UC) of near-infrared light (980 nm) to ultra-violet (360 nm), blue (450 and 475 nm), red (650 and 695 nm) and infrared (800 nm) light in the β-NaYF₄ : Yb,Tm nanocrystals has been studied by UC spectroscopy. Both the total intensity of UC emissions and the relative intensities of emissions at different wavelengths have shown a strong dependence on different particle sizes and different Tm³⁺ and Yb³⁺ concentrations. As a result, different overall output colors of UC emissions can be achieved by altering sizes and Yb³⁺/Tm³⁺ doping concentrations of the β-NaYF₄ : Yb,Tm nanocrystals. The intensity-power curves of a series of samples have proved that emissions at 360 and 450 nm can be ascribed to four-photon process (¹D₂ to ³H₆ and ¹D₂ to ³H₄, respectively), while emissions at 475 and 650 nm are three-photon processes (¹G₄ to ³H₆ and ¹G₄ to ³H₄, respectively) and emissions at 695 and 800 nm are two-photon ones (³F₂ to ³H₆ and ³F₄ to ³H₆, respectively). A UC saturation effect would occur under a certain excitation intensity of the 980 nm CW diode laser for the as-obtained β-NaYF₄ : Yb,Tm nanocrystals, leading to the decrease of the slopes of the I–P curves. The results of our study also revealed that the successive transfer model instead of the cooperative sensitization model can be applied to explain the UC behaviors of the β-NaYF₄ : Yb,Tm nanocrystals. Further, an unexpected stronger emissions of four-photon process at 360 and 450 nm for ∼50 nm β-NaYF₄ : Yb,Tm nanocrystals than those for the bigger (∼150 nm) nanocrystals was observed and explained in terms of the effects of crystallite size, surface-to-volume ratio and homogeneity of the doping cations.