Li2TiO3:Mn4+ Deep‐Red Phosphor for the Lifetime‐Based Luminescence Thermometry

Abstract

Luminescence of monoclinic lithium metatitanate (Li2TiO3) powders activated with different quantities of Mn4+ is studied in detail. Its strong deep-red emission arising from the Mn4+ 2Eg → 4A2g spin forbidden transition is centered at around 688 nm and is suitable for luminescence thermometry. Structural and electron paramagnetic resonance analyses show that Mn4+ ions are equally distributed in two almost identical Ti4+ sites in which they are octahedrally coordinated by six oxygen ions. Calculations based on the exchange charge model of the crystal field provided values of Racah parameters (B=760 cm−1, C= 2993 cm−1), crystal-field splitting Dq= 2043 cm−1, and the nephelauxetic parameter β1=0.9775. The maximal quantum efficiency of 24.1% at room temperature is found for 0.126% Mn4+ concentration. Temperature quenching of emission occurs by a cross-over via 4T2 excited state of the Mn4+ ions with T1/2=262 K and is quite favorable for the application in the lifetime-based luminescence thermometry since relative changes in emission decay values are exceptionally-large (around 3.21% at room temperature). We derived theoretical expressions for the temperature dependence of the absolute and relative sensitivities and discuss the influence of host material properties on lifetime sensitivities. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim