Journal
JOURNAL OF MATERIALS CHEMISTRY C
Volume 10, Issue 16, Pages 6380-6391Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2tc00485b
Keywords
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Funding
- Spanish Ministerio de Ciencia e Innovacion [PGC2018-101464-B-I00, BES-2016-077449]
- Spanish Ministerio de Ciencia e Innovacion (MALTAConsolider Team) [RED2018-102612-T]
- Ministry of Science and Higher Education of the Russian Federation as a part of the State Assignment of the Kurnakov Institute of General and Inorganic Chemistry
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This study presents a spectroscopic investigation of doubly Mn4+ and Cr3+-doped Sr4Al14O25 to evaluate its potential as a red emitting phosphor. The results show that Sr4Al14O25 exhibits a ruby-like emission due to the strong crystal field effect of Cr3+. The photoluminescence and excitation spectra of Sr4Al14O25:Mn4+,Cr3+ reveal a non-centrosymmetric distorted Al4 site in the crystal structure. Additionally, the study highlights the effects of pressure and temperature on the photoluminescence intensity and lifetime of the material.
We present a spectroscopic study of the doubly Mn4+ and Cr3+-doped Sr4Al14O25, synthesised via solid state reaction, as a function of pressure and temperature to check its potential as a red emitting phosphor. The strong crystal field acting on Cr3+ yields a ruby-like narrow R-line emission that is used as an intrinsic temperature sensor and, in comparison to ruby, provides a fair estimate of the bulk modulus K = 172 GPa for Sr4Al14O25. The photoluminescence (PL) and associated excitation spectra of Sr4Al14O25:Mn4+,Cr3+ unravel a strong-field 3d(3) configuration with R-1 and R-2 emission lines largely separated by 10.7 meV, which characterizes the non-centrosymmetric distorted Al4 site in the Sr4Al14O25 structure. Eighteen Raman modes have been detected at ambient pressure. They correspond to the stretching modes of the Al-O bonds and show frequency shifts with pressure consistent with Gruneisen parameters (gamma = 0.65), similar to those measured for other aluminates. The variations of PL intensity and lifetime with temperature exhibit a similar concomitant behaviour indicating an efficient pumping to the T-4(2) level and hence down to the E-2 emitting level in both Mn4+ and Cr3+ ions at low and moderate temperatures. Multiphonon non-radiative processes yield a quenching temperature of 400 K for Mn4+ with an effective activation energy of 0.57 eV. Unexpectedly, this energy decreases with pressure enhancing the non-radiative processes and thus PL intensity reduction. A thoroughly coordinate configurational energy diagram is presented for explaining the main spectroscopic features and excited-state dynamics.
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