Understanding the structure-property relationship and optimizing properties of phosphors for use in lighting and scintillation fields is an important materials challenge. In this work, we investigated the effects of the pH value of the coprecipitating solution adjusted by the concentration of NHOH(aq) on the structure and optical properties of the obtained LaHfO nanoparticles (NPs). The obtained NPs stabilize in the ideal pyrochlore structure, but the extent of ordering increased with an increase in the pH value used. The NPs prepared at pH = 12.1 displayed the best optical performance owing to the balance of the crystallinity, agglomeration, and surface defects. On the basis of density functional theory (DFT) calculations, the origin of violet-blue emission in undoped LaHfO NPs was attributed to defect states in the electronic band gap arising due to oxygen defects. For the LaHfO:Eu NPs, the Eu dopants possess low symmetry and their occupancy is more favorable at the LaO site. DFT calculations further justify the complete host-to-dopant energy transfer and origin of the most intense red emission observed experimentally. Understanding the interplay of the experimental and theoretical results thus is a very useful general approach for improving the efficiency of luminescent materials.

Doping induced phase transformation and speciation of the uranium ions in La2Hf2O7 nanoparticles as nuclear waste host were investigated.

High temperature annealed La2Hf2O7:Eu3+ nanoparticles favor tunneling of Eu3+ to symmetric sites showing orange emission, whereas low temperature annealed samples favor red emission.

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Ln 3+ -ion-doped nanomaterials possess excellent properties because of their high color purity, longer excited state lifetime, narrow emission, and large Stokes shifts. In this work, we studied the correlation between the luminescence properties of La 2 Hf 2 O 7 :Eu 3+ pyrochlore nanoparticles (NPs) synthesized by a molten salt synthesis (MSS) method at a relatively low temperature and several MSS processing durations (from 1 to 12 h). We synthesized these NPs with different sizes just by changing the MSS processing time without subjecting to high temperature. Raman spectroscopy confirmed the stabilization of the ideal pyrochlore structure of the La 2 Hf 2 O 7 :Eu 3+ NPs at various MSS processing durations. The synthesized NPs exhibited bright red emission under UV, visible, and X-ray excitations, highlighting their potential applications as a red phosphor and scintillator. As the MSS processing time was increased from 1 to 12 h, a spectral change in the position of the charge transfer state in the La 2 Hf 2 O 7 :Eu 3+ NPs was observed. The sample processed by the MSS with a duration of 3 h exhibited the highest luminescence intensity, which was attributed to its optimum crystals with least surface defects and less agglomeration. The obtained results strongly and unambiguously indicate the brighter side of this new type of pyrochlore-based NPs in the fast growing field of solid-state lighting and scintillator materials.

Crystal structure has a strong influence on the luminescence properties of lanthanide-doped materials. In this work, we have investigated the thermally induced structural transition in Gd 2 Hf 2 O 7 (GHO) using Eu 3+ ions as the spectroscopic probe. It was found that complete phase transition from the disordered fluorite phase (DFP) to the ordered pyrochlore phase (OPP) can be achieved in GHO with the increase of annealing temperature from 650 → 1100 → 1300 °C. OPP is the more stable structural form for the GHOE nanoparticles (NPs) annealed at a higher temperature based on the energy calculation by density functional theory (DFT). The asymmetry ratio of the GHOE-650 NPs was the highest, whereas the quantum yield, luminescence intensity, and lifetime values of the GHOE-1300 NPs were the highest. Emission intensity of Eu 3+ ions increases significantly with the phase transition from the DFP to OPP phase and is attributed to the higher radiative transition rate (281 s –1 ) of the 5 D 0 level of the Eu 3+ ion in the environment with relatively lower symmetry ( C 2 v ) because of the increase of crystal size. As the structure changes from DFP to OPP, radioluminescence showed tunable color change from red to orange. The Eu 3+ local structure obtained from DFT calculation confirmed the absence of inversion symmetry in the DFP structure, which is consistent with the experimental emission spectra and Stark components. We also elucidated the host to dopant optical energy transfer through density of states calculations. Overall, our current studies present important observations for the GHOE NPs: (i) thermally induced order–disorder phase transition, (ii) change of point group symmetry around Eu 3+ ions in the two phases, (iii) high thermal stability, and (iv) tunability of radioluminescent color. This work provides fundamental understanding of the relationship between the crystal structure and photophysical properties of lanthanide-doped materials and helps design a strategy for advanced optoelectronic materials.

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