XANES analysis of phosphate glasses melted with Tb4O7 and SnO: evaluating the impact of valence states on structural, thermal, and luminescent properties

Abstract

Barium phosphate glasses were prepared with 0.5 mol% Tb₄O₇ added alongside SnO up to 5 mol% with the purpose of evaluating the resulting terbium and tin oxidation states and their impact on glass structural, thermal, and luminescent properties. Following material synthesis by melt-quenching, the composition-structure–property investigation was pursued encompassing measurements by X-ray diffraction (XRD), X-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, differential scanning calorimetry (DSC), dilatometry, and photoluminescence (PL) spectroscopy. While XRD confirmed the amorphous nature of the glasses, results from XANES indicated that terbium occurs as terbium(III) with a predisposition for tin to exist as tin(IV) which decreased at high SnO content. The structural as well as the thermal properties appeared to be mostly impacted by the presence of tin(IV). Specifically, glass depolymerization was indicated to be induced by Sn⁴⁺ ions, and their concentration was observed to correlate with glass transition and softening temperatures. On the other hand, the tin(II) remnants were observed to exert an impact on the luminescent properties shifting light emission from the green towards the blue-green (cyan). It is indicated that Tb₄O₇ reacting to produce Tb₂O₃ supports the oxidation of tin(II) to tin(IV) which in turn dominates the physical properties. However, this was somewhat circumvented at the highest SnO content wherein tin(IV) appeared to be lower.