• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2769-2773
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• 2013

Red phosphors $Ca_{(1-1.5x)}Eu_xWO_4$ and $Ca_{(1-2x)}Eu^_xNa_xWO_4$ were synthesized with various concentrations x of $Eu^{3+}$ ions by using a solid-state reaction method. The crystal structure of the red phosphors were found to be a tetragonal scheelite structure with space group $I4_1/a$. X-ray diffraction (XRD) results show the (112) main diffraction peak centered at $2{\theta}=28.71^{\circ}$, and indicate that there is no basic structural deformation caused by the vacancies ${V_{Ca}}^{{\prime}{\prime}}$ or the $Eu^{3+}$ (and $Na^+$) ions in the host crystals. Densities of $Ca_{(1-1.5x)}Eu_xWO_4$ were measured on a (helium) gas pycnometer. Comparative results between the experimental and theoretical densities reveal that $Eu^{3+}$ (and $Na^+$) ions replace the $Ca^{2+}$ ions in the host $CaWO_4$. Also, the photoluminescence (PL) emission and photoluminescence excitation (PLE) spectra show the optical properties of trivalent $Eu^{3+}$ ions, not of divalent $Eu^{2+}$. Raman spectra exhibit that, without showing any difference before and after the doping of activators to the host material $CaWO_4$, all the gerade normal modes occur at the identical frequencies with the same shapes and weaker intensities after the substitution. However, the FT-IR spectra show that some of the ungerade normal modes have shifted positions and different shapes, caused by different masses of $Eu^{3+}$ ions (or $Na^+$ ions, or ${V_{Ca}}^{{\prime}{\prime}}$ vacancies) from $Ca^{2+}$.

• Journal of the Korean Ceramic Society
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• v.43 no.1 s.284
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• pp.10-15
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• 2006

Photoluminescence (PL) and crystal structures of the $(l-x)CaWO_4-xLi_2WO_4$ binary system added with $Eu_2O_3$ activator have been characterized. The $CaWO_4\;and\;Li_2WO_4$ have the scheelite and phenakite structures respectively. The $CaWO_4-Li_2WO_4-Eu_2O_3$ phosphors show the red luminescence of 613 nm peak wavelength. The wavelength range of excitation spectral band is $380\~470$ nm with the peak wavelength of 397 nm. The $0.88(0.5CaWO_4-0.5Li_2WO_4)-0.12Eu_2O_3$ showed the most superior luminescence characteristics. The effect of co-doping elements such as $Al_2O_3$ and rare-earth oxides on PL has been characterized. The co-doping elements deteriorated the luminescence intensity except the $Al_2O_3$ and $Gd_2O_3$. The PL characteristics of $CaWO_4-Li_2WO_4-Eu_2O_3$ phosphors have been compared to those of the alkali europium double molybdates (tungstates) of scheelite-related structure such as $LiEu(MoO_4)_2$ and $CsEu(MoO_4)_2$. The crystal structures of $(l-y)[(l-x)CaWO_4-xLi_2WO_4]-yEu_2O_3$ phosphors have been characterized using XRD data and rietveld refinement.

• Korean Journal of Materials Research
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• v.22 no.5
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• pp.215-219
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• 2012

Red phosphors $Ca_{1-1.5x}WO_4:{Eu_x}^{3+}$ were synthesized with different concentrations of $Eu^{3+}$ ions by using a solid-state reaction method. The crystal structure of the red phosphors was found to be a tetragonal system. X-ray diffraction (XRD) results showed the (112) main diffraction peak centered at $2{\theta}=28.71^{\circ}$, and the size of crystalline particles exhibited an overall decreasing tendency according to the concentration of $Eu^{3+}$ ions. The excitation spectra of all the phosphors were composed of a broad band centered at 275 nm in the range of 230-310 nm due to $O^{2-}{\rightarrow}W^{6+}$ and a narrow band having a peak at 307 nm caused by $O^{2-}{\rightarrow}Eu^{3+}$. Also, the excitation spectrum presents several strong lines in the range of 305-420 nm, which are assigned to the 4f-4f transitions of the $Eu^{3+}$ ion. In the case of the emission spectrum, all the phosphor powders, irrespective of $Eu^{3+}$ ion concentration, indicated an orange emission peak at 594 nm and a strong red emission spectrum centered at 615 nm, with two weak lines at 648 and 700 nm. The highest red emission intensity occurred at x = 0.10 mol of Eu3+ ion concentration with an asymmetry ratio of 12.5. Especially, the presence of $Eu^{3+}$ in the $Ca_{1-1.5x}WO_4:{Eu_x}^{3+}$ shows very effective use of excitation energy in the range of 305-420 nm, and finally yields a strong emission of red light.