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Spectral Properties and Thermal Quenching of Mn⁴⁺ Luminescence in Silicate Garnet Hosts CaY₂MgMAlSi₂O₁₂ (M=Al, Ga, Sc) ^*

DOI: 10.21883/FTT.2019.05.47600.02F

Переводная версия: 10.1134/S1063783419050147

Kirm M.¹, Oja M.¹, Kozlova J.¹, Mandar H.¹, Vielhauer S.¹, Jansen T.², Justel T.², Khaidukov N.M.³, Makhov V.N.⁴

¹Institute of Physics, University of Tartu, Tartu, Estonia

²Munster University of Applied Sciences, Steinfurt, Germany Münster University of Applied Sciences, Steinfurt, Germany

³N.S. Kurnakov Institute of General and Inorganic Chemistry, Moscow, Russia

⁴P.N. Lebedev Physical Institute, Moscow, Russia

Email: makhov@sci.lebedev.ru

Выставление онлайн: 19 апреля 2019 г.

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Multi-component silicate garnet ceramics CaY₂MgMAlSi₂O₁₂ comprising different cations M=Al, Ga or Sc in octahedral sites doped with Mn⁴⁺ ions have been synthesized and studied as novel red-emitting phosphors aiming at warm white pc-LED applications. All synthesized phosphors exhibit Mn⁴⁺ luminescence in rather deep red region, the shortest-wavelength spectrum of Mn⁴⁺ luminescence (peak wavelength at 668 nm) being obtained for the host with the largest cation M³⁺=Sc³⁺ in the octahedral site. The effect of increasing the energy of the emitting Mn⁴⁺ ²E level with the size of the host cation in octahedral sites is supposed to be the result of decrease of the covalence of the "Mn⁴⁺-ligand" bonding with increase of the interionic Mn⁴⁺-O^2- distance. All studied phosphors demonstrate rather poor thermal stability of Mn⁴⁺ photoluminescence with a thermal quenching temperature T_1/2 below 200 K, the lowest value being observed for the host with M=Sc. As expected, the decrease of the energy of the O^2--Mn⁴⁺ charge-transfer state is observed with the increase of the M³⁺ cation radius, i. e. with the increase of the O^2--Mn⁴⁺ interionic distance. The thermal quenching temperature of Mn⁴⁺ luminescence in the studied phosphors correlates with the energy of the O^2--Mn⁴⁺ charge transfer state which is supposed to serve as a quenching state for Mn⁴⁺ luminescence. This research was performed within the ERA. Net RUS Plus Programme, project NANOLED # 361. Financial support from Russian Foundation for Basic Research (Grant Nos. 16-52-76028 ERA_a and 16-53-76027 ERA_a), Estonian Research Council (NANOLED) and BMBF (Germany, Grant No. 01DJ16004) is gratefully acknowledged by the Moscow, Tartu and Munster groups. The Tartu group also acknowledges financial support from the ERDF funding in Estonia granted to the Center of Excellence TK141 (project No. 2014-2020.4.01.15-0011) and from the Estonian Research Council grant PUT RG111.

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