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A new niobium-doped inorganic scintillating oxyfluoride, Rb4Ge5O9F6:Nb, was synthesized in single crystal form by high-temperature flux growth. The host structure, Rb4Ge5O9F6, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.98430(10) Å, b = 11.7265(2) Å, and c = 19.2732(3) Å, consisting of germanium oxyfluoride layers made up of Ge3O9 units connected by GeO3F3 octahedra. In its pure form, Rb4Ge5O9F6 shows neither luminescence nor scintillation but when doped with niobium, Rb4Ge5O9F6:Nb exhibits bright blue luminescence and scintillation. The isostructural doped structure, Rb4Ge5O9F6:Nb, crystallizes in the orthorhombic space group Pbcn with lattice parameters a = 6.9960(3) Å, b = 11.7464(6) Å, and c = 19.3341(9) Å. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements suggest that the niobium is located in an octahedral coordination environment. Optical measurements inform us that the niobium dopant acts as the activator. The synthesis, structure, and optical properties are reported, including radioluminescence (RL) measurements under X-ray irradiation. 

Symmetry-dependent properties such as ferroelectricity are suppressed at room temperature in Pb-free ABO 3 perovskites due to antiferrodistortive dynamics (octahedral rotations/tilts), resulting in the preferential stabilization of centrosymmetric crystals. For this reason, defect engineering (Ca doping, oxygen vacancy, etc. ) has been leveraged to break the symmetry of these crystals by inducing symmetry/structural transitions to modify the local A/B-site environment. This work demonstrates the use of in situ / ex situ photoluminescence spectroscopy to systematically detect symmetry/structural transformations in prototypical ferroelectric ABO 3 perovskites. These baseline optical responses are compared to recently synthesized Ca x Sr 1−x NbO 3 (CSNO) nanocrystals, which undergoes similar ferroelectric/structural phase transitions. Furthermore, the resultant PL response is corroborated with X-ray diffraction (XRD) and absorption spectroscopy (XAS) measurements to confirm the structural changes. This ability to directly monitor the local site symmetry within ABO 3 perovskites via photoluminescence spectroscopy can be used to screen for temperature- and defect-induced ferroelectric transitions.