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Inorg Chem. 2007 Aug 6;46(16):6329-37. Epub 2007 Jun 30.

Highly uniform and monodisperse beta-NaYF(4):Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: hydrothermal synthesis and luminescent properties.

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Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, PR China.


beta-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu3+ (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to 5D0-3 --> 7FJ (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively. When doped with 5% Tb3+ ions, the strong DC fluorescence corresponding to 5D4 --> 7FJ (J = 6, 5, 4, 3) transitions with 5D4 --> 7F5 (green emission at 544 nm) being the most prominent group that has been observed. In addition, under 980 nm laser excitation, the Yb3+/Er3+- and Yb3+/Tm3+-codoped beta-NaYF4 samples exhibit bright green and whitish blue up-conversion (UC) luminescence, respectively. The luminescence mechanisms for the doped lanthanide ions were thoroughly analyzed.

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