LaF3:Yb^3+ , Er^+ microcrystals were synthesized by a hydrothermal method, and then, the LaF3: Yb^3+ , Er^+ microcrystals were coated with silica. Phase identification of LaF3: Yb^3+ , Er^+ and LaF3: Yb^3+ , Er^+/SiO2 was performed via XRD. The TEM image showed that the size of LaF3: Yb^3+ , Er^+ was 150 nm and LaF3: Yb^3+ , Er^+/SiO2 presented clearly a core/shell structure with 20 nm shell thickness. The upconversion spectra of LaF3: Yb^3+ , Er^+ and LaF3: Yb^3+ , Er^+/SiO2 in solid state and in ethanol were studied with a 980 nm diode laser as the excitation source. The upconversion spectra showed that the silica shell had little effect on the properties of fluorescence of the LaF3:Yb^3+ , Er^+ microcrystals. At the same time, the green luminescence photo of LaF3: Yb3+, Er3+/SiO2 in the PBS buffer was obtained, which indicated that the LaF3: Yb^3+ , Er^+/SiO2 could be used in biological applications.
Cubic NaYF4:Yb^3+(20%)/Er^3+(1%) microspheres were synthesized by EDTA-assisted hydrothermal method. Under 980 nm excitation, ultraviolet (^4G11/2→^4I15/2), violet (^2H9/2→^4I15/2), green (^4F7/2→^4I15/2, 2H11/2→^4I15/2, and ^4S3/2→^4I15/2), and red (^4F9/2→^4I15/2) upconversion fluorescence were observed. The number of laser photons absorbed in one upconversion excitation process, n, was determined to be 3.89, 1.61, 2.55, and 1.09 for the ultraviolet, violet, green, and red emissions, respectively. Obviously, n=3.89 indicated that a four-photon process was involved in populating the ^4G11/2 state, and n=2.55 indicated that a three-photon process was involved in populating the ^4F7/2/^2H11/2/^4S3/2 levels. For the violet and red emissions, the population of the states ^2H9/2 and ^4F9/2 separately came from three-photon and two-photon processes. The decrease of n was well explained by the mechanism of competition between linear decay and upconversion processes for the depletion of the intermediate excited states.
Recently, considerable attention has been paid to the synthesis and research of various rare-earth (RE) doped fluoride nanomaterials because of their high refractive index and appropriate phonon energy, which have potential applications in optics, optoelectronics, microelectronics, and tribology. Many methods have been utilized to synthesize the nanomaterials of RE doped fluorides with controllable sizes, shapes, and nanostructures. Comparatively, the microwave irradiation (MWI) method is simple, fast, and unique in its potential for large-scale synthesis without suffering thermal gradient effects.
Unusual intense infrared-to-ultraviolet upconversion luminescence was observed in YF3:yb3+(20%)/Tm3+(1%) nanocrystals under 980 ran excitation. The intense ultraviolet emissions (1I6→^3H6, ^1I6→3F4, and ^1D2→^3H6) were affirmed arisillg from the excitation processes of five-photon and four-photon. In comparison with the bulk sample with the same chemical compositions, ultraviolet upconversion luminescence of the nanocrystals was markedly enhanced. Spectral analysis indicated that the enhancement was attributed to the decrease of Judd-Ofelt parameter Ω2, which precluded the transition rate from 3F2 to 3F4, enhanced the energy transfer process and populated the ^1D2 level: ^3F2→^3H6 (Tm^3+): 3H4→^1D2 (Tm^3+).