Synthesis of NaLn(WO4)2 phosphors via a new phase-conversion protocol and investigation of up/down conversion photoluminescence

Abstract

The two-dimensional (2D) crystallite morphology and low OH−/Ln3+ molar ratio of Ln2(OH)4SO4·2H2O (Ln = lanthanide) make it an ideal precursor for materials synthesis via phase conversion, which was manifested in this work by the direct generation of well-defined NaLn(WO4)2 phosphor particles via hydrothermal reaction with Na2WO4. Kinetics study showed that pure NaLn(WO4)2 can be produced by reaction at 180 °C for ~24 h or at 200 °C for ~6 h under WO42−/Ln3+ = 10 M ratio. Morphology analysis revealed that, though NaLn(WO4)2 evolved via re-precipitation, the layered crystal structure and 2D crystallite morphology of the precursor could have templated the nucleation/growth of NaLn(WO4)2, leading to uniform particles (~4–5 μm) of a unique microdisc-like morphology. Under 394 nm excitation, the Ln = La0.95Eu0.05 phosphor showed down-conversion luminescence having an absolute quantum yield of ~35.4%, a fluorescence lifetime of ~1.13 ms for its 616 nm main emission, and color coordinates of around (0.63, 0.37). Under 978 nm laser excitation, the Ln = La0.97Yb0.02Ho0.01 and Ln = La0.97Yb0.02Er0.01 phosphors exhibited the strongest up-conversion (UC) luminescence at ~660 nm (the 5F5 → 5I8 transition of Ho3+) and 551 nm (the 4S3/2 → 4I15/2 transition of Er3+), average fluorescence lifetimes of ~178.3 and 82.3 µs for the above emissions, and chromaticity coordinates of around (0.62, 0.38) and (0.25, 0.72), respectively. The two UC phosphors were also analyzed to exhibit UC luminescence through a two-photon mechanism.