Characterization of various Eu2+ sites in Ca2SiO4:Eu2+ and Ba2SiO4:Eu2+ by high-pressure spectroscopy

Photoluminescence of Ba₂SiO₄ and Ca₂SiO₄ activated with Eu²⁺ was investigated at various temperatures (from 10 K to 300 K) and pressures (from ambient to 200 kbar). At ambient pressure and room temperature, under UV excitation both phosphors yielded a green emission band with maxima at 505 nm and 510 nm for Ba₂SiO₄ and Ca₂SiO₄, respectively. The energies of these bands depended on pressure; the pressure shifts were ?12:55 cm^?1/kbar for Ba₂SiO₄:Eu²⁺; and ?5:59 cm^?1/kbar for Ca₂SiO₄:Eu²⁺. In the case of Ca₂SiO₄:Eu²⁺, we observed additional broadband emission at lower energies with a maximum at 610 nm (orange band). The orange and green emission in Ca₂SiO₄:Eu²⁺ had different excitation spectra: the green band could be excited at wavelengths shorter than 470 nm, whereas the orange band — at wavelengths shorter than 520 nm. The pressure caused a red shift of orange emission of 7.83 cm^?1/kbar. The emission peaked at 510 nm was attributed to the 4f⁶5d→4f⁷(⁸S₇₌₂) transition of Eu²⁺ in the β — Ca₂SiO₄:Eu²⁺ phase, whereas the emission peaked at 610 nm — to the γ — Ca₂SiO₄:Eu²⁺ phase. The emission of Ba₂SiO₄:Eu²⁺ peaked at 505 nm was attributed to the 4f⁶5d→ 4f⁷(⁸S_7/2) transition of Eu²⁺ in the β — Ba₂SiO₄ phase.