Structural study of rare earth doped fluoride phosphate glasses by solid-state nuclear magnetic resonance

Abstract

A series of glasses with the compositions of 10NaF-(90-x) NaPO3-xYF3 (x = 5, 10, 15 and 20 mol%) were prepared via the conventional melt-quenching method. The structures of these glasses were characterized by multiple advanced solid-state nuclear magnetic resonance (SSNMR) techniques. Multiple phosphorus species QmnY were resolved at atomic level. Here, the value m and n denote the number of P–O–P bonds and the number of Y3+ ion bounding to phosphorus oxygen tetrahedron, respectively, which were identified by two dimensional (2D) J-resolved spectroscopy. 19F MAS spectra, 19F↔23Na and 19F↔31P rotational echo double resonance (REDOR) prove that F−ions are involved into the glass networks through Y-F•••Na and P-F•••Na linkages. The 31P {19F} J-coupling based heteronuclear multiple quantum coherence (J-HMQC) spectrum proves that F− ions selectively connect with Q1 species. F− ions show significant preference to connecting with Y3+ over P5+.