For applications such as near-infrared (NIR) spectroscopy requiring energy-efficient and compact broadband NIR light sources, a variety of Ni2+-doped phosphors emitting in the 1100–2000 nm range has been developed. However, the commercialization of Ni2+-doped NIR phosphors has not yet been achieved, and material exploration is ongoing. To gain insight into the luminescence properties of Ni2+, including emission wavelength and efficiency influenced by compositional and structural variations, Ni2+-doped double-perovskite AELaMgTaO6:Ni2+ (AE = Ba, Sr, or Ca) ceramic samples were synthesized, and their optical properties were examined. Because the energy of the Ni2+ 3d-3d transition is sensitive to structural variations in the local environment around the Ni2+ ions, we investigated the variation in optical properties by indirect ligand field engineering of NiO6 octahedra following the substitution of alkaline earth ions AE2+. The prepared AELaMgTaO6:Ni2+ samples were Ba-Sr or Ba-Ca complete solid solution systems with cubic-to-monoclinic phase transitions. The broad NIR luminescence band at ∼1350–1700 nm was blue-shifted by ∼100 nm, accompanied by Sr2+ or Ca2+ substitution. The local symmetry of the NiO6 octahedra was reduced from Oh to Ci owing to the phase transition, resulting in an enhancement of the NIR luminescence intensity and an increase in the quenching temperature. This study demonstrated that Ni2+ phosphors with the desired optical properties for NIR spectroscopy applications can be designed by controlling the composition ratio of the host compounds and the resultant variation in the local environment of the solid solution compounds.
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