An Apatite-Group Praseodymium Carbonate Fluoroxybritholite: Hydrothermal Synthesis, Crystal Structure, and Implications for Natural and Synthetic Britholites.

Britholites are the lanthanide-silica-rich end-members of the apatite group, commonly studied for their optical properties. Here, we show ∼50-100 µm single crystals synthesized hydrothermally at 650-500 °C and 500-300 MPa composed of a solid solution between Ca2Pr3(SiO4)3F-fluorbritholite and CaPr4(SiO4)3O-oxybritholite, with a significant carbonate component substitution, via C4+ replacing Si4+. Single-crystal X-ray diffraction and density functional theory computations show that a planar carbonate group occupies the face of a now-vacant silica tetrahedron. This modifies Pr-O bond lengths, diversifying lanthanide optical emission wavelengths. Our britholite was synthesized in geologically reasonable conditions and compositions, suggesting that carbonated oxybritholites could exist as yet-unrecognized natural minerals.

Co-Doping Effect of Mn2+ and Eu3+ on Luminescence in Strontiowhitlockite Phosphors.

A new series of Sr-based phosphates, Sr9-xMnxEu(PO4)7, were synthesized using the high-temperature solid-state method in air. It was found that these compounds have the same structure as strontiowhitlockite, which is a ß-Ca3(PO4)2 (or ß-TCP) structure. The concentration of Mn2+ ions required to form a pure strontiowhitlockite phase was determined. An unusual partial reduction of Eu3+ to Eu2+ in air was observed and confirmed by photoluminescence (PL) and electron spin resonance (ESR) spectra measurements. The PL spectra recorded under 370 nm excitation showed transitions of both 4f5d-4f Eu2+ and 4f-4f Eu3+. The total integral intensity of the PL spectra, monitored at 395 nm, decreased with increasing Mn2+ concentration due to quenching effect of Eu3+ by the Mn2+ levels. The temperature dependence of Eu2+ photoluminescence in a Sr9-xMnxEu(PO4)7 host was investigated. The conditions for the reduction of Eu3+ to Eu2+ in air were discussed.