Pycnometric and Spectroscopic Studies of Red Phosphors Ca2+(1-1.5x)WO4:Eu3+x and Ca2+(1-2x)WO4:Eu3+x,Na+x

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 $Ca^{2+}$.