Selective doping of Ni2+ in octahedral sites provided by nanocrystals embedded in glass-ceramics (GCs) is crucial to the enhancement of broadband near-infrared (NIR) emission. In this work, a NIR emission with a full-width-at-half-maximum (FWHM) of 288 nm is first reported from ZnGa2O4: Ni2+ nano-spinels embedded GCs with excellent transparency. A comparison is made of the NIR luminescence properties of Ni2+ doped GCs containing ZnGa2O4, germanium-substituted ZnGa2O4 nano-spinels (Zn1+xGa2−2xGexO4), and Zn2GeO4/Li2Ge4O9 composite nanocrystals that are free of Ga3+. The results show that ZnGa2O4: Ni2+ GCs exhibit a significantly enhanced NIR emission. The incorporation of the nucleating agent TiO2 is favored in terms of the increased luminescence intensity and prolonged lifetime. The possible causes for the enhancement effect are identified from the crystal structure/defects viewpoint. The newly developed GCs incorporate good reproducibility to allow for a tolerance of thermal treatment temperature and hence hold great potential of fiberization via the recently proposed “melt-in-tube” method. They can be considered as promising candidates for broadband fiber amplifiers.

Selective doping of optically active ions into the nanocrystalline phase(s) of glass ceramics is of interest for photoluminescence (PL) applications to control the energy transfer (ET) processes between dopants on the nanometer length scale. Here, the focus is on explaining the essential knowledge of the distribution of two groups of active ions: transition metal (Ni2+ and Cr3+) and rare earth (Yb3+ and Er3+) ions, which are doped into i) single‐phase Ga2O3 and ii) dual‐phase Ga2O3 and YF3 nanocrystals (NCs). These NCs are obtained by thermally crystallizing ternary silicate‐ and quinary fluorosilicate‐based glasses, respectively. It is found that the two types of active ions can successfully be doped into Ga2O3 NCs, resulting in enhanced ET between the dopants because of the small separation distance of, e.g., <10 Å, whereas ET is significantly suppressed when Ga2O3 and YF3 NCs are coprecipitated. In this case, the studied rare earth ions have a high propensity for being selectively doped in YF3 NCs. The studied transition‐metal ions can always be found in Ga2O3 NCs irrespective of the presence of the fluoride phase. The selective doping and the ET between the two types of active ions can be controlled simultaneously on annealing. This may allow for the achievement of diverse PL properties, such as ultrabroadband near‐infrared and upconversion‐mediated Stokes emissions.

The partitioning of rare earth ions (REs: Yb3+, Er3+, Eu3+ and Nd3+) in γ-Ga2O3 nanocrystals (NCs) precipitated in a nanostructured silicate glass ceramic is revealed, and the enrichment of REs in the NCs (bulk doping) rather than on the interfaces between the NCs and the surrounding glassy phase (surface doping) is differentiated.

Defects present ubiquitously in glasses exert a strong influence on the optical qualities and performances of glass, a phenomenon that has not been well studied to date.

Ni2+/Yb3+/Er3+/Tm3+ codoped transparent glass‐ceramics (GCs) containing both hexagonal β‐YF3 and spinel‐like γ‐Ga2O3 dual‐phase nanoparticles (NCs) are synthesized by melt‐quenching and subsequent heating procedures. Two techniques of transmission electron microscopy (TEM) nanoanalytics and optical spectroscopy are conjugated to understand the distribution of the rare‐earth ions (REs) and transition metals (TMs) in the nanostructured GCs. It is found that the REs are located predominantly in β‐YF3, whereas the TMs in γ‐Ga2O3 NCs. As a result, energy transfer (ET) between the REs and TMs is considerably suppressed due to the large spatial separation (> 3 nm), but it is enhanced between the REs partitioned in the β‐YF3 NCs. This has important implications for intended and demanding photoluminescence functions. For example, an ultrabroadband near‐infrared (NIR) emission in the wavelength region of 1000‐2000 nm covering the entire telecommunications window is observed for the first time. Meanwhile, intense upconversion (UC) emissions covering the 3 primary colors and locating in the first biological window can be also recorded under excitation by a single pump source at 980 nm.