5d–4f luminescence of Ce3+, Gd3+ and Lu3+ in LiCaAlF6

The emission and excitation spectra as well as decay kinetics of luminescence due to 5d–4f transitions in Ce³⁺, Gd³⁺ and Lu³⁺ ions doped into LiCaAlF₆ crystals have been analyzed with high spectral and time resolution using synchrotron radiation for excitation. The rich fine structure originating from electronic origins of transitions and their phonon replica has been well resolved and identified. Experimental data are compared with the spectra simulated in the framework of the semiphenomenological models of the crystal field and the crystal lattice dynamics.     

Spectral properties of Pr3+ ions in Bi2(MoO4)3 crystal

A Bi₂(MoO₄)₃ single crystal doped with Pr³⁺ ions has been grown by the Czochralski technique. The polarized absorption and fluorescence spectra as well as the fluorescence decay curve of Pr³⁺ ions in the crystal were measured at room temperature. The spectroscopic parameters, including the Judd–Ofelt intensity parameters Ω_t (t=2, 4, and 6), spontaneous emission probabilities, fluorescence branching ratios, radiative lifetimes, stimulated emission cross sections, and fluorescence quantum efficiencies, were calculated. The spectral properties related to laser performance of this crystal were analyzed. The ¹ D ₂ multiplet of the crystal may be a good upper level for a solid-state laser.     

Luminescence and scintillation of Eu2+‐doped high silica glass

High silica glass doped with Eu²⁺ ions was prepared as a scintillating material by impregnation of Eu ions into a porous silica glass followed by reduction sintering in CO atmosphere. A dominant emission band of the Eu²⁺ 5d–4f transition peaking around 430 nm was observed in the luminescence spectrum with the excitation peak around 280 nm and no emission from Eu³⁺ was present. Photoluminescence decay kinetics was governed by decay times of a few microseconds. The Eu²⁺‐doped high silica glass exhibited comparable energy resolution and slightly higher photoelectron yield with respect to the Bi₄Ge₃O₁₂ crystal in the pulse height spectra for X‐ray photon energies within 22–60 keV. Furthermore, a factor of 1.2 higher radioluminescence intensity was observed as well. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of charge compensation by means of Na+ ions on the luminescence behavior of Sm3+-doped CaAl4O7 phosphor

Results of structural and spectroscopic measurements of Sm³⁺ doped calcium aluminates: Ca_1?xSm_xAl₄O₇ and Ca_1?2xSm_xNa_xAl₄O₇ (x=0.0005, 0.002, 0.01, 0.02, 0.03, 0.05) obtained by the modified Pechini method are presented. All samples yield intense orange–red emission under violet excitation (404.5 nm). Narrow bands corresponding to characteristic f–f intraconfigurational transition of Sm³⁺ in excitation and emission spectra were observed. The influences of the concentration of Sm³⁺ as well as charge compensation by co-doping with Na⁺ ions on the luminescent properties of the phosphor were investigated. Detailed analysis of the emission spectra of Sm³⁺ doped and Sm³⁺,Na⁺ co-doped CaAl₄O₇ powders proved that activator ions substitute Ca²⁺ in the host. Co-doping with Na⁺ ions enhanced greatly the intensity of the luminescence. Concentration dependencies of the intensity of luminescence and its decay kinetics proved the emission quenching at higher dopant contents due to cross-relaxation processes between Sm³⁺ ions. Fitting of the ⁴G_5/2 state fluorescence decay to the Inokuti–Hirayama model indicated dipole–dipole interaction as the dominant mechanism of the cross-relaxation processes.     

Luminescence spectroscopy of Ce3+-doped ABaPO4 (A=Li, Na, K) phosphors

Ce³⁺ doped ABaPO₄ (A=Li, Na, K) phosphors were prepared by conventional high temperature solid-state reaction. The phosphors were investigated by XRD, photoluminescence excitation and emission spectra, and luminescence decay curves. The five 5d levels corresponding to the 4f¹→4f⁰5d¹ transition of Ce³⁺ ions were identified. The spectroscopic parameters, e.g., the 5d barycenter, the crystal-field splitting, and the Stokes shift, were discussed. LiBaPO₄:Ce³⁺ phosphor could be efficiently excited by the near-UV lights (330–420 nm) and showed a broad emission band in the range of 430–620 nm with the maximum wavelength at 468 nm. In contrast, Ce³⁺-doped NaBaPO₄ and KBaPO₄ showed only excitation bands in a limited UV region (230–370 nm) and have blue emission at 385 nm and 416 nm, respectively. The temperature quenching of luminescence and the chromaticity coordinates were reported. The luminescence properties were discussed by analyzing the crystal structure and the local surroundings of Ce³⁺ ions on the Ba²⁺ sites.     

Polarized spectral analysis of Er3+ ions in biaxial Bi2(MoO4)3 crystal

An Er³⁺:Bi₂(MoO₄)₃ single crystal has been grown by the Czochralski technique. The Stark sublevels of the ⁴I_15/2 and ⁴I_13/2 multiplets of Er³⁺ ions in the crystal were determined. The polarized absorption spectra, polarized fluorescence spectra, and fluorescence decay curve of the crystal were measured at room temperature and the relevant spectroscopic parameters, including the Judd–Ofelt intensity parameters, spontaneous emission probability, fluorescence branching ratio, radiative lifetime, and stimulated emission cross section, were estimated. The effect of re-absorption on the spectroscopic parameters was discussed. When the crystal was excited at 977 nm, up-conversion green fluorescence was observed and discussed.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Growth, spectroscopic characteristics and laser potential of Yb3+:Ca3La2(BO3)4 crystal

Crystal of Yb³⁺-doped Ca₃La₂(BO₃)₄ has been grown by the Czochralski technique. The room temperature absorption and fluorescence spectra of the crystal have been investigated. The result showed that this crystal exhibits broad absorption and emission with the FWHM of 11 nm at 978 nm and 66 nm FWHM at 1025 nm, respectively. The stimulated emission cross-section of Yb³⁺ ions were calculated using the reciprocity method and Fuchtbauer-Ladenburg method, respectively. The room temperature fluorescence decay curves of ² F _5/2 manifold of Yb³⁺ ions were recorded for both crystal and powder samples. The effect of radiation tapping on the spectroscopic properties is discussed. The result that the lifetime of the powder sample is shorter than that of the bulk sample demonstrates the existence of radiation trapping effect. The laser potentiality was also evaluated and the results show that this crystal is a good candidate for tunable and ultrashort pulse lasers.     

Vacuum ultraviolet 5d14f9-4f10 emission of Ho3+ ions in alkaline-earth fluorides

Time-resolved emission and excitation spectra as well as emission decay kinetics of CaF₂, SrF₂, BaF₂ doped with HoF₃ were investigated. Intensive emission bands near 168 nm, having long decay time, are caused by the spin-forbidden transitions from the 5d¹4f⁹ high-spin states to the ground ⁵I₈ states of Ho³⁺ ions. Weak spin allowed 5d¹4f⁹(low-spin)-4f¹⁰ emission band at 158 nm was observed only in CaF₂–Ho crystals. Spin allowed and spin-forbidden excitation bands were observed near 166 and 155 nm, respectively, in all studied crystals. Fast component of spin-forbidden emissions due to multiphonon relaxation to low-lying 4f¹⁰ Ho³⁺ level also was observed for all crystals.     

Synthesis and spectroscopy of sodium-gadolinium tungstate NaGd(WO4)2 crystals activated by Tm3+ ions

Single crystals of disordered double sodium-gadolinium tungstate NaGd(WO₄)₂ doped with Tm ions were grown by the Czochralski method. The polarized absorption and emission spectra of these crystals with different activator concentrations and the decay kinetics of the ³ H ₄ and ³ F ₄ excited states of Tm³⁺ ions at 300 K were investigated. The absorption and emission cross sections of the expected laser transition ³ F ₄ ? ³ H ₆ in the Tm³⁺ ion were determined and the amplification spectra of the active laser medium NaGd(WO₄)₂:Tm at different levels of inverse population of the upper laser level ³ F ₄ of the Tm³⁺ ion were constructed. The prospects for using these crystals as active media in 2-μm solid-state lasers are discussed.     

Evaluation of Ce3+ and alkali metal ions Co-doped LiSrAlF6 crystalline scintillators

High scintillation efficiency of Eu-doped LiSrAlF₆ (LiSAF) and LiCaAlF₆ (LiCAF) codoped with alkali metal ions has been reported in our recent studies. Thus in this paper, we demonstrated the scintillation properties of 1% Ce-doped LiSAF crystals with 1% alkali metal ions co-doping to increase the light yield and understand the scintillation mechanism. The crystals showed intense emission band corresponding to the 5d-4f transition of Ce³⁺, and their light yields under thermal neutron excitation were higher than that of the Ce only doped crystal. Especially, the light yield of Ce–Na co-doped crystal exceeded about two times that of Ce only doped one.     

Luminescence of calcium orthoborate doped by Ce3+ ions

The luminescence properties of calcium orthoborate Ca₃(BO₃)₂ doped with cerium are studied upon x-ray (～30 keV) and VUV (3.5–15 eV) synchrotron excitation. The emission bands peaked at 392 and 420 nm are attributed to interconfigurational transitions of Ce³⁺ ions. The short-wavelength emission band at 340 nm is caused by radiative decay of exciton-like states. The fundamental absorption edge of Ca₃(BO₃)₂ is found to be near 7.1 eV. Based on thermoluminescence data and other information, the behavior of defects in Ca₃(BO₃)₂:Ce³⁺ is studied.     

Comparative study of Tm-doped and Tm-Sc co-doped Lu3Al5O12 scintillator

The crystals of Tm doped and Tm-Sc co-doped Lu₃Al₅O₁₂ (LuAG) grown by the floating zone (FZ) method were examined for their optical and scintillation properties. In transmittance spectra, strong absorption lines due to Tm³⁺ 4f–4f transitions were observed. X-ray excited radioluminescence spectra were measured and broad and sharp emission peaks were detected. The former one was attributed to Sc³⁺ and the latter one was due to Tm³⁺ 4f–4f transitions. Scintillation yield enhancement due to Sc co-doping was observed by means of ¹³⁷Cs pulse height spectra. Scintillation decay times were several tens of μs under pulse X-ray excitation.     

Optical transitions of Eu2+ IONS in RbMgF3 crystals

Because of the need for tunable solid state lasers in the blue region of the spectrum, a number of recent studies have been on the optical properties of Eu²⁺ in various crystals lattices. The absorption and emission from Eu²⁺ ions in fluoride hosts arise from both 5d→4f and 4f→4f transitions. The absorption is in the ultra-violet and the emission is in the blue. The 4f-4f transitions are very sharp and are located around 360 nm. The 5d→4f emission bands at 405 nm and 525 nm are broad and host lattice dependent. We have studied the temperature dependence of the optical properties of RbMgF₃:Eu²⁺ including absorption, emission, and excitation. In the case of the emission studies both temperature dependence and the lifetimes of the transitions have been measured. These transitions are discussed in detail.     

掺Nd3+激光玻璃的激光窄线选择激发

本文利用可调谐脉冲染料激光器的窄线输出,在低温和室温下,激发掺钕碲、锗、硅、磷酸盐玻璃和氟铍玻璃的⁴I_9/2→⁴G_5/2(²G_7/2)不均匀增宽吸收带。观测了荧光衰减对激发波长的关系,从而研究在不同玻璃基质中,处于不同格位的Nd³⁺离子的衰减特性以及他们之间的相互作用情况。 关键词：     

Optic characteristics of Pr3+ doped NaY(MoO4)2 crystal

The polarized absorption and emission spectra of Pr³⁺ ions in NaY(MoO₄)₂ single crystal were investigated. The standard and modified Judd–Ofelt theory have been applied to the measured optical absorption intensities to determine the spectroscopic parameters, including the Judd–Oflet intensity parameters Ω_t (t=2,4,6), the radiative transition rates, branching ratios, and emission cross-sections for various excited levels of Pr³⁺ ions. In samples with Pr³⁺ ions concentration of 2.00×10²⁰ cm^-3, the excitation of the ¹ D ₂ manifold decays non-radiatively by the electric dipole–dipole transfer between Pr³⁺ neighbors. The good spectroscopic properties show the possible application of the Pr³⁺ doped NaY(MoO₄)₂ crystal as a solid-state laser. PACS 42.70.Hj; 78.20.-e     

Synthesis and characterization of fast-decaying bluish green phosphors of Tb3+-doped CaSi2O2N2 for 2D/3D plasma display panels

Oxynitride phosphor powders comprising of CaSi₂O₂N₂ doped with Tb³⁺ were successfully synthesized using a high-temperature solid-state reaction method. The experimentally determined photoluminescence (PL) properties of the produced phosphors meet the requirements of 2D/3D plasma display panels (PDPs). In particular, under the excitation of vacuum ultraviolet (VUV) synchrotron radiation and ultraviolet (UV) irradiation, emission peaks corresponding to the ⁵D₃→⁷F_J (J=6, 5, 4, 3) and ⁵D₄→⁷F_J (J=6, 5, 4, 3) transitions of Tb³⁺ ions were recorded. Monitoring the ⁵D₄→⁷F₅ emission of Tb³⁺ at 545 nm, the excitation bands were assigned to the host-related absorption as well as the 4f–5d (fd) and the 4f–4f (ff) transitions of Tb³⁺. The produced phosphors can be efficiently excited at 147 nm, and have an adequately short decay time (τ_1/10=1.14 ms).     

Effect of Na+ co-dopant and activator concentration on luminescent properties of CaGa4O7:Eu3+

Two series of calcium gallate phosphors: Ca_1?xEu_xGa₄O₇ and Ca_1?2xEu_xNa_xGa₄O₇ (x=0, 0.002, 0.01, 0.02, 0.03, 0.05) were synthesized by a modified Pechini method and their optical properties at 298 and 77 K were investigated. In undoped CaGa₄O₇ upon 255 nm excitation a bluish white emission (λ_max=500 nm) followed by an afterglow of the same color lasting for 10–20 s was observed. Eu³⁺-doping quenched the host-related luminescence and the characteristic red emission of the dopant with maximum at 613 nm appeared. Its excitation spectrum consisted of a broad band assigned to ligand to metal, O^2?→Eu³⁺, charge transfer absorption and narrow lines arising from intraconfigurational transitions within the 4f⁶ states of Eu³⁺ ion. The effects of Eu³⁺ concentration and Na⁺ co-doping on the luminescence properties and decay kinetics were studied. Low temperature emission spectra showed that Eu³⁺ ions are positioned in environments of different symmetries. Their relative populations changed with the activator content. Co-doping with Na⁺ ions led to a remarkable reduction of the number of Eu³⁺ sites as well as to noticeable improvement of the luminescence brightness though it did not affect the decay time of the emission. The quantum efficiencies of singly doped CaGa₄O₇:Eu³⁺ were very low (in the range of 1–3.7%). Na⁺ co-doping improved this parameter leading to the highest efficiency of 11% for CaGa₄O₇:3%Eu³⁺,3%Na⁺.     

Spectroscopic analysis of Pr3+:CaYAlO4 crystal

The polarized absorption, emission spectra and decay time measurements of Pr³⁺-doped CaYAlO₄ single crystal have been performed at room temperature. Based on the Judd–Ofelt theory, the spectroscopic parameters \(\Upomega_{t} (t = 2,4,6)\) , radiative transition probabilities, radiative lifetimes and branching ratios were obtained. The stimulated emission cross-section, fluorescence lifetimes and the quantum efficiency of the promising laser transition were also calculated and compared with other reported crystals. The results show that Pr³⁺:CaYAlO₄ is a promising candidate for visible solid-state laser emission.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.