The metastable garnet lattice of Gd3Al5O12 (GdAG) was effectively stabilized via doping with significantly smaller Lu3+, and based on which (Gd,Lu)AG:Yb/Ho was developed in this work as a new type of upconversion phosphor. The phosphor particles calcined from the precursors synthesized via carbonate precipitation were observed to have good dispersion and fairly uniform morphologies. Optical spectroscopy found that the [(Gd1-xLux)0.948Yb0.05Ho0.002]3Al5O12 (x=0.1-0.5) garnet powders exhibit a green emission centered at ~543 nm (the 5F4,5S25I8 transition of Ho3+) and a red emission centered at ~668 nm (the 5F55I8 transition of Ho3+) under laser excitation at 978 nm. The upconversion emission intensity was found to decrease with increasing Lu3+ doping. Meanwhile, the dependence of up-conversion emission intensity on the pumping power was measured and the up-conversion mechanism was discussed in detail. The Yb/Ho codoped (Gd,Lu)AG garnet system developed herein may potentially be used as a new type of luminescent material.
To suppress the thermal decomposition and to stabilize the crystal structure of Gd3Al5O12 (GdAG) garnet, doping GdAG with smaller Ln3+ (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, respectively) to form (Gd,Ln)AG solid solutions was proposed in work. Carbonate precursors of (Gd,Ln)AG with an approximate composition of (NH4)x(Gd,Ln)3Al5(OH)y(CO3)z•nH2O were synthesized via coprecipitation from a mixed solution of ammonium aluminum sulfate and rare earth nitrate, using ammonium hydrogen carbonate as the precipitant. The precursors and the calcination derived oxides were characterized using FT-IR spectroscopy, DTA/TG, XRD, BET and FE-SEM. The results showed that smaller Ln3+ doping can indeed stabilize GdAG against its thermal decomposition to a mixture of GdAlO3 (GdAP) and Al2O3 phases at elevated temperatures and at the same time effectively lowers the temperature for garnet crystallization. The carbonate precursors are loosely agglomerated and the resultant (Gd,Ln)AG powders show good dispersion and a fairly uniform particle morphology. The (Gd,Ln)AG solid solutions exhibit decreasing lattice parameters along with decreasing radius of the dopant ions at the same dopant content of 50 at%. Photoluminescence properties of some of the garnet solid solutions are also studied. The materials developed herein may potentially be used for photoluminescent and scintillation applications.
A series of layered rare-earth hydroxides (LRHs) of (Y,Ln)2(OH)5NO3•nH2O ( Ln=Tb,Eu), have been synthesized via a hydrothermal route. Crystal structures and optical properties of the materials have been investigated in detail by the combined techniques of XRD, FT-IR, FE-SEM, HR-TEM, and PLE/PL spectroscopies. It is shown that Tb3+ and Eu3+ are successfully incorporated into the Y-LRH host lattice to form solid solutions. Under UV excitation, the binary (Y0.97Tb0.03)- and (Y0.97Eu0.03)-LRHs exhibit their respective characteristic photoluminescence of the Eu3+ and Tb3+ activators. The ternary (Y0.965Eu0.005Tb0.03)-LRH simultaneously shows red and green emissions and both the intensity and emission color can be adjusted by changing the excitation wavelength. Compared with (Y0.995Eu0.005)-LRH, the ternary (Y0.965Eu0.005Tb0.03)-LRH exhibits appreciably enhanced 615nm red-emission, which indicates the existence of non- radiative energy transfer from Tb3+ to Eu3+. The ternary (Y0.965Eu0.005Tb0.03)-LRH also readily undergoes anion exchange with a series of inorganic and organic anions at room temperature.
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