Optical Spectroscopy and Excited-State Dynamics of Eu³⁺-Doped Bismuth Borate Glasses Containing CuO

Bismuth borate glasses containing phosphors and luminescent rare-earths are of interest for applications in light-emitting devices. Herein, the influence of CuO impurities on red-emitting Eu³⁺-doped bismuth borate glasses of the 25Bi₂O₃-15BaO-10Li₂O-50B₂O₃ type was investigated by various spectroscopic methods. The glasses were prepared by the melt-quench technique and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV/Vis optical absorption (OA), and photoluminescence (PL) spectroscopy including decay kinetics assessment. The XRD data confirmed the amorphous nature of the glasses whereas FT-IR spectra indicated the basic structural features of trigonal BO₃ units and BO₄ tetrahedra. The OA analysis showed that addition of CuO up to 0.5 mol% results in significant growth of the visible Cu²⁺ absorption band around 715 nm, with slight decrease in the optical band gap energies assessed through Tauc plots. A drastic PL quenching of Eu³⁺ ions emission was evidenced concurring with the detrimental effect of Cu²⁺. The assessment of the Eu³⁺ emission decay curves revealed significant lifetime decrease of the ⁵D₀ emitting state with increasing CuO concentration. An analysis of quenching constants was finally performed comparing results from integrated PL data with the emission decay rates. It is argued that the bismuth borate glass system supports an effective Eu³⁺→Cu²⁺ energy transfer (more so than phosphates) in connection with a strong spectral overlap between Eu³⁺ emission and Cu²⁺ absorption.