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Influence of Sc substitution on the structure and properties of NASICON-type Na 3 Sc 2- x R x (PO 4 ) 3 (R = Eu, Tb, Dy) phosphors.

Nataliya R KrutyakDmitry A SpasskyIrina KudryavtsevaEldar M GallyamovDaria G FilatovaAleksandr V MosunovVladimir A Morozov
Published in: Dalton transactions (Cambridge, England : 2003) (2024)
Na 3 Sc 2- x R x (PO 4 ) 3 (R = Eu, Tb, Dy; 0 ≤ x ≤ 0.2) phosphors were synthesized by a high-temperature solid-state reaction. Sc : R ratios for the NSP: x R samples were determined by ICP-MS, EDX-SEM and TEM-EDX measurements. An X-ray diffraction study revealed that solid solutions with a NASICON-type structure were formed at 0 ≤ x ≤ 0.1. The luminescence properties of Na 3 Sc 2 (PO 4 ) 3 and Na 3 Sc 2- x R x (PO 4 ) 3 (R = Eu, Tb, Dy) were studied in the range of 80-500 K. The highest R 3+ luminescence intensity in Na 3 Sc 2- x R x (PO 4 ) 3 (R = Eu, Tb, Dy) depending on R was found for x = 0.05 in the case of Dy and x = 0.1 in the case of Eu and Tb. The temperature behaviour of the R 3+ emission intensity of Na 3 Sc 2- x R x (PO 4 ) 3 (R = Eu, Tb, Dy) depends on R that replaces Sc. The decrease of the Eu 3+ emission intensity depending on the transition energy by ∼26% and 18% at ∼420 K compared to T R allowed us to consider NSP:0.1Eu 3+ as a suitable phosphor for pc-LEDs. The temperature dependence of the Dy 3+ emission for NSP:0.05Dy 3+ demonstrates a strong thermal quenching. Different temperature dependences of the Tb 3+ emission intensity of NSP:0.1Tb 3+ were found for two excitation bands at λ ex = 220 and 378 nm representing f-d and f-f intracentre transitions. No thermal quenching for f-f transitions takes place while the emission intensity for f-d transitions increases with a temperature rise from 80 to 500 K. The dielectric measurements for Na 3 Sc 2 (PO 4 ) 3 and Na 3 Sc 1.9 Eu 0.1 (PO 4 ) 3 were provided on ceramic pellets sintered under vacuum using a spark plasma sintering technique. Different dependences of conductivity were found for two samples. The calculated conductivity for Na 3 Sc 1.9 Eu 0.1 (PO 4 ) 3 with an R 3̄ c structure ( σ bulk = 6.4 × 10 -5 S cm -1 at 300 K, 1.14 × 10 -3 S cm -1 at 360 K and 5.0 × 10 -2 S cm -1 at 500 K) is higher than that for pure α-Na 3 Sc 2 (PO 4 ) 3 but lower than that for β- and γ-Na 3 Sc 2 (PO 4 ) 3 .
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