Luminescence properties of Yb:Nd:Tm:KY3F10 nanophosphor and thermal treatment effects

Abstract In this work, we present the spectroscopic properties of KY 3 F 10 (KY3F) nanocrystals activated with thulium and codoped with ytterbium and neodymium ions. The most important processes that lead to the thulium upconversion emissions in the blue region were identified. A time-resolved luminescence spectroscopy technique was employed to measure the luminescence decays and to determine the most important mechanisms involved in the upconversion process that populates 1 G 4 (Tm 3+ ) excited states. Analysis of the energy-transfer processes dynamics using selective pulsed-laser excitations in Yb:Nd:Tm, Nd:KY3F nanocrystals shows that the direct energy transfer from Nd 3+ to Tm 3+ ions is the mechanism responsible for the 78% of the blue upconversion luminescence in the Yb:Nd:Tm:KY3F when compared with the Yb:Nd:Tm:KY3F bulk crystal for an laser excitation at 802 nm. An investigation of the 1 G 4 level luminescence kinetic of Tm 3+ in Yb/Nd/Tm system revealed that the luminescence efficiency ( 1 G 4 ) starts with a very low value (0.38%) for the synthesized nanocrystal (as grown) and strongly increases to 97% after thermal treatment at 550 °C for 6 h under argon flow. As a consequence of the thermal treatment at T =550 °C, the contributions of the (Nd×Tm) (Up 1 ) and (Nd×Yb×Tm) (Up 2 ) upconversion processes to the 1 G 4 luminescence are 33% (Up 1 ) and 67% for Up 2 . Up 2 process represented by Nd 3+ ( 4 F 3/2 )→Yb 3+ ( 2 F 7/2 ) followed by Yb 3+ ( 2 F 5/2 )→Tm ( 3 H 4 )→Tm 3+ ( 1 G 4 ) was previously reported as the main mechanism to produce the blue luminescence in Yb:Nd:Tm:YLiF 4 and KY 3 F 10 bulk crystals. Results of X-ray diffraction analysis of nanopowder using the Rietveld method reveled that crystallite sizes remain unchanged (12–14 nm) after thermal treatments with T ≤400 °C, while the 1 G 4 luminescence efficiency strongly increases from 0.38% ( T =25 °C) to 12% ( T =400 °C). Results shown that the Nd 3+ ions distribution has a concentration gradient increasing towards the nanoparticle surface allowing the direct (Nd×Tm) (Up 1 ) (78%) in competition with the (Nd×Yb×Tm) (Up 2 ) (22%) upconversions for the synthesized nanocrystals (11 nm).