Temperature-induced phase transition and tunable luminescence properties of Ce3+-Mn2+-Zr4+ tri-doped LaPO4 phosphor

Abstract

Tunable blue-white-orange emitting LaPO4:Ce3+/Mn2+/Zr4+ (LPCMZ) phosphors have been synthesized by co-precipitation followed by calcination. The X-ray diffraction (XRD) shows the phase transition from hexagonal to monoclinic between 600 and 700 °C, accompanied by the increase of average nanocrystallites size from 8 to 64 nm. The Raman measurements revealed the vibrational modes associated with the LPCMZ crystalline phases, where the band positions and the full width at half maximum values depend on the structural parameters and nanocrystals size. For low-temperature calcination of 500 °C, scanning electron microscopy (SEM) revealed nanoclusters composed of thinner nanoneedles, which developed into a rod-like self-assembly shape for higher calcination temperatures at around 900 °C. Electron paramagnetic resonance (EPR) spectroscopy reveals a broad isotropic EPR signal, assigned to agglomerated/clustered Mn2+ ions, which are dispersed only at high temperatures above 900 °C. The photoluminescence spectra recorded under UV-excitation of Ce3+ ions showed the Mn2+ green/red (546, 630 nm) emissions due to an energy transfer (ET) between Ce3+ and Mn2+. Depending on the calcination temperature, the Mn2+ emission color can be finely adjusted from blue to white and orange.