Persistent luminescence mechanism of tantalite phosphors

[摘要] Pr3+ ion doped ZnTa2O6, SrTa2O6, CaTa2O6 and ZnTaGaO5 phosphors, which display persistentluminescence were prepared by solid state chemical reaction at 1200 oC for 4 hours. AZnTa2O6:Pr3+ phosphor that resembled an orthorhombic single phase was obtained, as identifiedby X-ray diffraction (XRD). ZnTa2O6:Pr3+ displayed both blue and red emission, with the blueemission spectral line observed at 448 nm from the 3P0 �?3H4 transition, and the red spectrallines observed at 608, 619 and 639 nm from the 1D2 �?3H4, 3P0 �?3H6 and 3P0 �?3F2 transitions,respectively. For different concentrations of Pr3+, a concentration of 0.4 mol% Pr3+ provedsuitable to generate a phosphor displaying only red emission with the Commission Internationalede l'Eclairage (CIE) coordinates matching those of an ideal red color. Enhancement of theluminescence intensity of ZnTa2O6:Pr3+ phosphor was achieved by preparing it in the presence ofLi2SO4 and Li2CO3, which act as flux agents. The strong absorption by the defect levels due tothe flux was observed from the diffused reflectance spectra. Pr exists in both Pr3+ and Pr4+oxidation states as revealed by the X-ray photoelectron spectroscopy data. The presence of Pr3+increased, while Pr4+ decreased in the samples prepared in the presence of a flux. The increasedabsorption by the defect levels and the reduction of Pr4+ in the samples prepared using a fluxresulted in the enhancement of the luminescence intensity as observed from thephotoluminescence spectra. The lifetime of the persistent luminescence of ZnTa2O6:Pr3+ preparedin a flux was calculated using a second order exponential decay curve from the measuredphosphorescence decay curves. This showed an enhancement in the lifetime of the persistentluminescence of the fluxed sample, which is attributed to the additional electron trapping centresinduced by the flux as observed from the thermoluminescence glow curves. Additional means ofenhancing the lifetime of the persistent luminescence were achieved by co-doping ZnTa2O6:Pr3+with Li+, Na+, K+ or Cs+ ions, and by also incorporating gallium ions to form a new hostZnTaGa5:Pr3+. The scanning electron microscopy (SEM) images showed that particles were ofirregular shape and with different sizes. The preparation with the fluxing material showed andincreased particle sizes. The SEM images of ZnTaGa5:Pr3+ showed a surface morphology that iscomposed of particles with different shapes, including the irregular, rhombus and rod shapes.The distribution of the ions in the material was investigated using the Time of Flight Secondary Ion Mass Spectroscopy (ToF SIMS) surface maps, which showed that the ions were uniformlydistributed throughout the matrix. This showed successful incorporation of the ions. Pr3+ exhibitsprominent red emission in most oxide phosphors, which comes from the 1D2 �?3H4 transition,and greenish-blue emission from 3P0 �?3H4,5 transitions is normally less intense. However, agreenish-blue emission was observed from the CaTa2O6:Pr3+ oxide phosphor prepared by solidstate reaction at 1200 oC. A combination of emission coming from 1D2 and 3P0 levels wasobserved, with the blue emission from the latter much more prominent. Upon investigating thethermoluminescence properties of the phosphor, the glow curves showed the presence of threedifferent types of electron trapping centres. Interesting properties of the trapping centres, such asthe competition between the trapping centres, pre-radiation effects and the calculation of theactivation energy were studied. The phosphorescence decay curves showed long lastingafterglow. Three SrTa2O6:Pr3 + phosphor samples with persistent emission properties wereprepared by solid state reaction at 1200, 1400 and 1500 oC. The crystal structure formationimproved with an increase in temperature as identified by XRD. The scanning electronmicroscopy images showed that the particles of the phosphor were agglomerated and co-meltingwas induced by increasing the synthesis temperature. The ion distribution in the phosphors wasdetermined using the time of flight secondary ion mass spectroscopy. The red emission wasobtained from the 1D2 �?H4 and the 3P0 �?H6 transitions at 608 and 619 nm, respectively. Themain absorption occurred at 225 nm (5.5 eV), and the band gap (Eg) calculations confirmed thatit corresponds to band-to-band excitation. The persistent emission time parameters (260 �?296 s)were calculated from the phosphorescence decay curves using the second order exponentialdecay equation. The corresponding electron trapping centres were identified using thethermoluminescence spectroscopy, and the activation energy was determined using the initialrise method.

[发布机构] University of the Free State