This study develops and successfully demonstrates visualization methods for the characterization of europium (Eu)-doped BaAl2O4 phosphors using X-ray nanoprobe techniques. X-ray fluorescence (XRF) mapping not only gives information on the elemental distributions but also clearly reveals the valence state distributions of the Eu2+ and Eu3+ ions. The accuracy of the estimated valence state distributions was examined by performing X-ray absorption spectroscopy (XAS) across the Eu L 3-edge (6.977 keV). The X-ray excited optical luminescence (XEOL) spectra exhibit different emission lines in the selected local areas. Their corresponding emission distributions can be obtained via XEOL mapping. The emission properties can be understood through correlation analysis. The results demonstrate that the main contribution to the luminescence intensity of the Eu-doped BaAl2O4 comes from the Eu2+ activator and the emission intensity will not be influenced by the concentration of Eu2+ or Eu3+ ions. It is anticipated that X-ray nanoprobes will open new avenues with significant characterization ability for unravelling the emission mechanisms of phosphor materials.

A synchrotron source offers the advantage of continuous and tunable x rays. Therefore, not only an X-ray nanoprobe can provide the desired spatial resolution to measure the elemental distribution of CaAlSiN3:Eu2+ via X-ray fluorescence mapping but X-ray absorption spectroscopy can also be used to unambiguously analyze the valence states of europium ions (Eu2+ or Eu3+) in different local areas. X-ray excited optical luminescence spectra exhibit only one red emission peak (∼650 nm) corresponding to the 4f65d1 to 4f7 transition of Eu2+, which reveals the fact that Eu2+ ions substitute perfectly for Ca2+ ions at the same site. Through detailed analysis, we demonstrated that the main contribution to the luminescence intensity of CASIN:Eu2+ comes from the Eu2+ activator in the product. We anticipate that X-ray nanoprobes will open new avenues with great characterization ability for studying the emission properties of CASIN:Eu2+.

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Effects of Al content on the formation and the photoluminescence properties of CaAlSiN3:Eu2+ phosphor (CASIN) were investigated by a combustion synthesis method. XRD (X-ray diffraction), combined with PL (photoluminescence), TEM-EDS (transmission electron microscope equipped with an energy-dispersive X-ray spectroscope), and SAED (selected area electron diffraction) measurements, show that the bar-like CASIN gives a stronger emission than the plate-like and agglomerated fine particles. The emission intensity increases as the Al content increased from Al = 0.2 to Al = 0.8, which resulted from the extent of formation of CASIN increases. Then, the emission intensity decreases as the Al content is increased from Al = 0.8 to Al = 1.5, which resulted from the transformation of morphology of CASIN and a large amount formation of AlN. In addition, the extent of formation of CASIN increases with increasing Al from Al = 0.2 to Al = 1.2 and begins to decrease as Al is further increased to 1.5, and thus the peak emission wavelength increases from 647 nm to 658 nm as the Al molar ratio is increased from 0.2 to 1.2 and begins to decrease when further increasing the Al molar ratio to 1.5, which resulted from the large amount of AlN formed.