Holistic Assessment of NIR-Emitting Nd<sup>3+</sup>-Activated Phosphate Glasses: A Structure–Property Relationship Study
José A. Jiménez
Abstract
High Resolution Image Download MS PowerPoint Slide Near-infrared (NIR)-emitting phosphate glasses containing Nd 3+ ions are attractive for applications in laser materials and solar spectral converters. The composition–structure–property relation in this type of glass system is thus of interest from fundamental and applied perspectives. In this work, Nd 3+ -containing glasses were made by melting with 50P 2 O 5 -(50 – x )BaO- x Nd 2 O 3 ( x = 0, 0.5, 1.0, 2.0, 3.0, 4.0 mol %) nominal compositions and studied comprehensively by density and related physical properties, X-ray diffraction (XRD), Raman spectroscopy, O 1s X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), dilatometry, ultraviolet–visible (UV–vis)–NIR optical absorption, and photoluminescence (PL) spectroscopy with decay dynamics assessment. The densities and molar volumes of the Nd 3+ -containing glasses generally increased with Nd 2 O 3 concentration also resulting in shorter Nd 3+ –Nd 3+ distances. XRD supported the amorphous nature of the glasses, whereas the Raman spectra evolution was indicative of glass depolymerization being induced by Nd 3+ ions. Oxygen (1s) and phosphorus (2p) analysis by XPS for the glass with 4.0 mol % Nd 2 O 3 agreed with the increase in nonbridging oxygens relative to the undoped host. DSC results showed that the glass transition temperatures increased with Nd 3+ concentration, with the glasses also displaying a decreased tendency toward crystallization. Dilatometry showed trends of increasing softening temperatures and decreasing thermal expansion coefficients with increasing Nd 2 O 3 content. A glass strengthening/tightening effect was then indicated to be induced by Nd 3+ with higher field strength compared to Ba 2+ ions. The UV–vis–NIR absorption by Nd 3+ ions increased consistently with Nd 3+ concentration. The UV–vis absorption edges of the Nd-containing glasses were also analyzed via Tauc and Urbach plots for comparison with the undoped host. Concerning the PL behavior, the Nd 3+ NIR emission intensity was highest for 1.0 mol % Nd 2 O 3 and decreased thereafter. The decay kinetics of the 4 F 3/2 emitting state in Nd 3+ ions analyzed revealed decreasing lifetimes where the decay rate analysis pointed to the prevalence of ion–ion excitation migration leading to PL quenching at high Nd 3+ concentrations.