An investigation of the structural and luminescent properties of the transparent germanate glass-ceramics co-doped with Ni²⁺/Er³⁺ for near-infrared optical fiber applications was presented. Modification of germanate glasses with 10–20 ZnO (mol.%) was focused to propose the additional heat treatment process controlled at 650 °C to obtain transparent glass-ceramics. The formation of 11 nm ZnGa₂O₄ nanocrystals was confirmed by the X-ray diffraction (XRD) method. It followed the glass network changes analyzed in detail (MIR—Mid Infrared spectroscopy) with an increasing heating time of precursor glass. The broadband 1000–1650 nm luminescence (λ_exc = 808 nm) was obtained as a result of Ni²⁺: ³T₂(³F) → ³A₂(³F) octahedral Ni²⁺ ions and Er³⁺: ⁴I_13/2 → ⁴I_15/2 radiative transitions and energy transfer from Ni²⁺ to Er³⁺ with the efficiency of 19%. Elaborated glass–nanocrystalline material is a very promising candidate for use as a core of broadband luminescence optical fibers.

Glass-ceramic is semi-novel material with many applications, but it is still problematic in obtaining fibers. This paper aims to develop a new glass-ceramic material that is a compromise between crystallization, thermal stability, and optical properties required for optical fiber technology. This compromise is made possible by an alternative method with a controlled crystallization process and a suitable choice of the chemical composition of the core material. In this way, the annealing process is eliminated, and the core material adopts a glass-ceramic character with high transparency directly in the drawing process. In the experiment, low phonon antimony-germanate-silicate glass (SGS) doped with Eu³⁺ ions and different concentrations of P₂O₅ were fabricated. The glass material crystallized during the cooling process under conditions similar to the drawing processes’. Thermal stability (DSC), X-ray photo analysis (XRD), and spectroscopic were measured. Eu³⁺ ions were used as spectral probes to determine the effect of P₂O₅ on the asymmetry ratio for the selected transitions (⁵D₀ → ⁷F₁ and ⁵D₀ → ⁷F₂). From the measurements, it was observed that the material produced exhibited amorphous or glass-ceramic properties, strongly dependent on the nucleator concentration. In addition, the conducted study confirmed that europium ions co-form the EuPO₄ structure during the cooling process from 730 °C to room temperature. Moreover, the asymmetry ratio was changed from over 4 to under 1. The result obtained confirms that the developed material has properties typical of transparent glass-ceramic while maintaining high thermal stability, which will enable the fabrication of fibers with the glass-ceramic core.