Abstract
In this work, the luminescence properties of undoped, Tm3+ doped, and Tb3+ plus Tm3+ double-doped crystals of the lithium magnesium phosphate (LiMgPO4, LMP) compound were investigated. The crystals under study were grown from melt using the micro-pulling-down method. The intrinsic and dopant-related luminescence of these crystals were studied using cathodo-, radio-, photo-, and thermoluminescence methods. Double doping with Tb3+ and Tm3+ ions was analyzed as these dopants are expected to exhibit an opposite trapping nature, namely to create the hole and electron-trapping sites, respectively. The spectra measured for the undoped samples revealed three prominent broad emission bands with maxima at around 3.50, 2.48, and 1.95 eV, which were associated with intrinsic structural defects within the studied compound. These were expected due to the anion vacancies forming F+-like centers while trapping the electrons. The spectra measured for Tb and Tm double-doped crystals showed characteristic peaks corresponding to the 4f–4f transitions of these dopants. A simplified model of a recombination mechanism was proposed to explain the temperature dependence of the measured thermally stimulated luminescence spectra. It seems that at low temperatures (below 300 °C), the charge carriers were released from 5D3-related Tb3+ trapping sites and recombination took place at Tm-related sites, giving rise to the characteristic emission of Tm3+ ions. At higher temperatures, above 300 °C, the electrons occupying the Tm3+-related trapping sites started to be released, and recombination took place at 5D4-related Tb3+ recombination centers, giving rise to the characteristic emission of Tb3+ ions. The model explains the temperature dependence observed for the luminescence emission from double-doped LiMgPO4 crystals and may be fully applicable for the consideration of emissions of other double-doped compounds.
Highlights
Stimulated luminescence phenomena are extensively exploited as great research tools in the basic research of materials [1,2]
TL is commonly known as a technique used in ionizing radiation dosimetry and dating, but it helps in the determination of luminescence mechanisms, trapping parameters, energy levels of defects in solid, etc
Small discrepancies in the relative intensities between the measured patterns and the reference were related to the presence of the Tb and Tm doping. They could be caused by the creation of structural defects, e.g., antisite defects, whose appearance is common in the case of melt-growth techniques, as well as by the preferred grain orientation induced by the sample preparation procedure
Summary
Stimulated luminescence phenomena are extensively exploited as great research tools in the basic research of materials [1,2] As these phenomena are extremely sensitive to defects in solids, they can, be utilized to study these defects. An example of the second category is a lattice vacancy caused by an impurity ion of a higher valence located at the position of a lattice ion (e.g., a trivalent cation impurity in a divalent lattice). This type of defect will induce the formation of a cation vacancy in the lattice to maintain charge neutrality. One can say that TL, together with the other abovementioned stimulated luminescence techniques, constitutes a complementary method in the field of materials research [4,5]
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