Cationic Effects on Photo- and X-ray Radioluminescence of K₃RE(PO₄)₂:Ce³⁺/Pr³⁺ (RE = La, Gd, and Y) Phosphors toward X-ray Detection

Cationic tuning for lanthanide (Ce3+/Pr3+)-activated inorganic phosphors with stable, efficient, and fast-decay 5d-4f emissions has emerged as an important strategy toward the continuing pursuit of superior scintillators. The in-depth understanding of the cationic effects on photo- and radioluminescence of lanthanides Ce3+ and Pr3+ centers is requisite for the rational cationic tuning. Here, we perform a systematic study on the structure and photo- and X-ray radioluminescence properties of K3RE(PO4)2:Ce3+/Pr3+ (RE = La, Gd, and Y) phosphors to elucidate the underlying cationic effects on their 4f-5d luminescence. By using the Rietveld refinements, low-temperature synchrotron-radiation vacuum ultraviolet-ultraviolet spectra, vibronic coupling analyses, and vacuum-referred binding energy schemes, the origins of lattice parameter evolutions, 5d excitation energies, 5d emission energies, and Stokes shifts as well as good emission thermal stabilities of K3RE(PO4)2:Ce3+ systems are revealed. In addition, the correlations of Pr3+ luminescence to Ce3+ in the same sites are also discussed. Finally, the X-ray excited luminescence manifests that the K3Gd(PO4)2:1%Ce3+ sample possesses a light yield of ∼10,217 photons/MeV, indicating its potentiality toward X-ray detection application. These results deepen the understanding of cationic effects on Ce3+ and Pr3+ 4f-5d luminescence and inspire the inorganic scintillator development.Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.RST/Luminescence Material

Insight into Eu redox and Pr³⁺ 5d emission in KSrPO₄ by VRBE scheme construction

A series of Ln-doped KSrPO4 (Ln = Ce3+, Eu3+, Eu2+, Pr3+) phosphors are prepared through a high-temperature solid-state method. The KSrPO4 compound is confirmed to possess a β-K2SO4 structure with the Pnma group by Rietveld refinement, and the temperature-dependent lattice parameters are investigated with the powder X-ray diffraction results at different temperatures. Ce3+ and Eu3+ ions are introduced to probe the crystal field strength (CFS) and the lanthanide site symmetry by using VUV-UV-vis spectroscopy. The temperature-dependent luminescence properties of KSrPO4: Ce3+/Eu2+ exhibit an excellent thermal stability of Ce3+/Eu2+ luminescence. Based on the VUV-UV-vis spectra of Ce3+ and Eu3+ doped KSrPO4, the vacuum referred binding energy (VRBE) scheme is constructed to understand the redox properties of Eu, the 5d energy levels of Pr3+ and the thermal quenching characteristics of Ce3+ and Eu2+ luminescence.Accepted Author ManuscriptRST/Fundamental Aspects of Materials and Energ

VUV-UV-vis photoluminescence, X-ray radioluminescence and energy transfer dynamics of Ce³⁺ and Eu²⁺ in Sr₂MgSi₂O₇

Ce3+ and Eu2+ doped and Ce3+-Eu2+ co-doped Sr2MgSi2O7 phosphors are prepared via a high-temperature solid-state reaction technique. The synchrotron radiation vacuum ultraviolet-ultraviolet (VUV-UV) excitation and ultraviolet-visible (UV-vis) emission spectra of diluted Ce3+ and Eu2+ doped Sr2MgSi2O7 samples are measured at cryogenic temperatures. The electron-vibrational interaction (EVI) between Ce3+ and its surroundings is analyzed. The dependencies of the 4f-5d transitions of Ce3+ on the structure of the host compounds Sr2MgSi2O7, Ba2MgSi2O7 and BaMg2Si2O7 are discussed in detail. Then the thermal quenching channel is proposed based on the measurements of temperature dependent luminescence intensities and decay times of Ce3+ and Eu2+ in Sr2MgSi2O7, and the Ce3+ → Eu2+ energy transfer mechanism is understood by three luminescence dynamic models. In addition, Sr2MgSi2O7:Ce3+/Eu2+ samples are evaluated for the possibilities of X-ray detection applications using X-ray excited luminescence (XEL) spectroscopy, and it was found that they are not suitable.Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.RST/Luminescence Material

Impacts of 5d electron binding energy and electron-phonon coupling on luminescence of Ce ³⁺ in Li ₆ Y(BO ₃ ) ₃

In this work, the crystal structure and electronic structure as well as the synchrotron radiation vacuum ultraviolet-ultraviolet-visible (VUV-UV-vis) luminescence properties of Li 6 Y(BO 3 ) 3 (LYBO):Ce 3+ phosphors were investigated in detail. The Rietveld refinement and DFT calculation reveal the P2 1 /c monoclinic crystal phase and the direct band gap of the LYBO compound, respectively. Only one kind of Ce 3+ 4f-5d transition is resolved in terms of the low temperature VUV-UV excitation, UV-vis emission spectra and luminescence decay curves. Furthermore, by constructing the vacuum referred binding energy (VRBE) scheme and applying the frequency-degenerate vibrational model, the impacts of 5d electron binding energy and electron-phonon coupling on luminescence of Ce 3+ in LYBO are analysed. The results show that the Ce 3+ emission in LYBO possesses a moderate intrinsic thermal stability. With the increase in concentration, the thermal stability of the emission gets worse due to the possible thermally-activated concentration quenching. In addition, the simulation of Ce 3+ emission profile at low temperature reveals that the 4f-5d electronic transitions of Ce 3+ ions can be treated to couple with one frequency-degenerate vibrational mode having the effective phonon energy of ∼257 cm −1 with the corresponding Huang-Rhys parameter of ∼6, which indicates a strong electron-phonon interaction of Ce 3+ luminescence in the Li 6 Y(BO 3 ) 3 host. Finally, the X-ray excited luminescence spectrum of the LYBO:5%Ce 3+ phosphor is measured to check the potential scintillator applications. RST/Luminescence Material

Experimental and Theoretical Studies of the Site Occupancy and Luminescence of Ce³⁺in LiSr₄(BO₃)₃for Potential X-ray Detecting Applications

Ce3+-doped LiSr4(BO3)3 phosphors have been prepared by a high-temperature solid-state reaction method, and structural refinement of the host compound has been performed. The excitation and emission spectra in the vacuum ultraviolet-ultraviolet-visible range at cryogenic temperatures reveal that Ce3+ ions preferentially occupy eight-coordinated Sr2+ sites in LiSr4(BO3)3. Such experimental attribution is well corroborated by the calculated 4f-5d transition energies and defect formation energies of Ce3+ ions at two distinct Sr2+ sites in the first-principles framework. In addition, the doping concentration-dependent luminescence and the temperature-dependent luminescence are systematically investigated by luminescence intensity and lifetime measurements, respectively. This shows that concentration quenching does not occur in the investigated doping range, but inhomogeneous broadening exists in the concentrated samples. With the estimated thermal quenching activation energy, the discussions on the thermal quenching mechanisms suggest that the thermal-ionization process of the 5d electron is a dominant channel for thermal quenching of Ce3+ luminescence, despite the fact that thermally activated concentration quenching cannot be excluded for the highly doped samples. Finally, the X-ray excited luminescence measurement demonstrates the promising applications of the phosphors in X-ray detection. Accepted Athor ManuscriptRST/Luminescence Material

Site Occupancies, VUV-UV-vis Photoluminescence, and X-ray Radioluminescence of Eu²⁺-Doped RbBaPO₄

RbBaPO4:Eu2+ phosphors have been prepared by a high-temperature solid-state reaction method, and the structure was determined by Rietveld refinement based on powder X-ray diffraction (P-XRD) data. Their VUV-UV-vis photoluminescence properties are systematically investigated with three objectives: (1) based on low-temperature spectra, we clarify the site occupancies of Eu2+, and demonstrate that the doublet emission bands at ∼406 and ∼431 nm originate from Eu2+ in Ba2+ [Eu2+(I)] and Rb+ [Eu2+(II)] sites, respectively; (2) an electron-vibrational interaction (EVI) analysis is conducted to estimate the Huang-Rhys factors, the zero-phonon lines (ZPLs) and the Stokes shifts of Eu2+ in Rb+ and Ba2+ sites; (3) the studies on luminescence decay of Eu2+(I) reveal that dipole-dipole interaction is mainly responsible for the energy transfer from Eu2+(I) to Eu2+(II), and the energy migration between Eu2+(I) is weak. Finally, the X-ray excited luminescence (XEL) spectrum indicates that the light yield of the sample RbBa0.995Eu0.005PO4 is ∼17700 ph/MeV, showing its potential application in X-ray detecting. Accepted Author ManuscriptRST/Luminescence Material