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Excitation-dependent local symmetry reversal in single host lattice Ba 2 A(BO 3 ) 2 :Eu 3+ [A = Mg and Ca] phosphors with tunable emission colours.
Physical Chemistry Chemical Physics : PCCP 2017 July 6
Eu3+ activated phosphors are widely used as red emitters in various display devices and light emitting diodes (LEDs). The emission characteristics of Eu3+ depend on the local site symmetry. The present study demonstrates the role of excitation-dependent local symmetry changes due to the structural reorganization on the emission colour tuning of Eu3+ from orange-red to orange in single host lattices, Ba2 Mg(BO3 )2 and Ba2 Ca(BO3 )2 . The choice of these lattices was based on the difference in the extent of strain experienced by the oxygen atoms. The samples with Eu3+ at Ba or Mg (Ca) sites were synthesized using the conventional high-temperature solid-state reaction method. The samples were characterized using powder XRD,11 B MAS-NMR, FT-IR, and diffuse reflectance UV-Vis spectroscopic techniques. The room temperature photoluminescence (PL) recorded using different excitation wavelengths revealed a clear difference in the PL emission features due to symmetry reversal from non-inversion to inversion symmetry around Eu3+ . The reorganization of highly strained oxygen atoms leads to such symmetry reversal. First-principles calculations were used to deduce the optimized structures of the two borate host lattices, and local geometries and their distortions upon Eu3+ substitution. The outcomes of these calculations support the experimental findings.
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