Luminescence-site symmetry correlations in Dy3+ doped alkali-alkaline earth orthoborates of the type XZBO3 with X = Li, Na, K and Z = Mg, Ca, Ba

Abstract

A systematic investigation of the luminescence properties of Dy3+ doped alkali-alkaline earth orthoborates of the stoichiometric composition XZBO3 with X = Li, Na, K and Z = Mg, Ca, Ba was conducted. XRD diffractograms show that the compounds LiMgBO3, LiCaBO3, LiBaBO3, NaMgBO3, NaCaBO3, NaBaBO3, and KMgBO3 could be produced in high purity. Relatively intense luminescence was observed only for the phases LiCaBO3, NaMgBO3, NaCaBO3 and NaBaBO3. Micro Raman investigations show that the Dy3+ luminesence mainly originates from the orthoborate phase in these samples. Photo-luminescence spectroscopy of LiCaBO3, NaCaBO3 and NaBaBO3 shows the typical Dy3+ emission with the prominent emission peak in the yellow spectral range around 575 nm. A second, but much less intense peak is observed at around 485 nm (cyan). The luminescence emission spectrum of Dy3+:NaMgBO3 is much different: here, the highest emission intensity is observed at about 485 nm. It is proposed that the Dy3+ ions occupy the Na positions in this crystal phase which has a much higher symmetry than the alkaline earth positions in the other examined crystal phases. This is supported by broadened and more split up peaks in the excitation and emission spectra of Dy3+:NaMgBO3 suggesting a much stronger local crystal field at the rare earth position in this compound. The results are additionally compared to spectroscopic data of different well known Dy3+ doped crystalline compounds and Dy3+ and Eu3+ doped alkali-alkaline earth orthoborates from other publications, which offer further insight into the relation between the crystallographic sites of the doped rare earth ions and their luminescence.