Deciphering the Nd3+ environment and energy-transfer mechanisms in thermally stable novel calcium aluminate glasses: elucidation of broadband high-gain performance for laser applications

Abstract

Rare-earth-doped barium calcium aluminate (BCA) glasses, having extended infrared (IR) transmission (6 μm), are attractive materials for near IR (NIR) photonic applications. Nd2O3-doped BCA glasses display broadband emission at 1.07 µm, but they are limited, with poor glass-forming ability (GFA) and low emission cross sections. In the present study, four different barium zinc calcium aluminate (BZCA) glasses are synthesized with varied ZnO concentrations (from 9.5 to 24.5 mol%) and doped with 0.5 mol% Nd2O3 to decipher the effect on GFA and spectroscopic properties. The addition of ZnO enhances the GFA, and the NdBZCA20 glass shows the maximum GFA. Ultraviolet (UV)–visible (Vis)–NIR absorption spectra reveal a decreasing trend in the nephelauxetic effect, while J–O parameters, emission, and gain properties lead to no significant alteration with increasing ZnO, and the structure–properties correlation is established accordingly. However, the emission cross sections for all ZnO concentrations are found ∼4.5 × 10−20 cm2 accompanied by broadband emission (Δλ eff ∼ 40 nm), which ensures the potentiality of these glasses for low-threshold high-gain laser applications as well as ultrashort pulse laser applications. Furthermore, a thorough analysis of 1.06 µm emission as a function of Nd concentration in the BZCA20 glass is reported here. The emission spectra and decay time indicate that 0.5 mol% is the optimized doping concentration. Inokuti–Hirayama and Burshtein equations are adopted to study the decay kinetics and energy-transfer mechanisms, which confirm that the energy-transfer process due to cross-relaxation is dominant up to 0.5 mol% concentration, whereas, beyond that concentration, excitation energy migration via the hopping mechanism supersedes.