Luminescence of Ce and Pr doped Sr2Mg(BO3)2 under VUV-UV and X-ray excitation

This report presents the luminescence properties of Ce³⁺ and Pr³⁺ activated Sr₂Mg(BO₃)₂ under VUV-UV and X-ray excitation. The five excitation bands of crystal field split 5d states are observed at about 46 729, 44 643, 41 667, 38 314 and 29 762 cm⁻¹ (i.e. 214, 224, 240, 261 and 336 nm) for Ce³⁺ in the host lattice. The doublet Ce³⁺ 5d→4f emission bands were found at about 25 840 and 24 096 cm⁻¹ (387 and 415 nm). The influence of doping concentration and temperature on the emission characteristics and the decay time of Ce³⁺ in Sr₂Mg(BO₃)₂ were investigated. For Pr³⁺ doped samples, the lowest 5d excitation band was observed at about 42017 cm⁻¹ (238 nm), a dominant band at around 35714 cm⁻¹ (280 nm) and two shoulder bands were seen in the emission spectra. The excitation and emission spectra of Ce³⁺ and Pr³⁺ were compared and discussed. The X-ray excited luminescence studies show that the light yields are ∼3200±230 and ∼1400±100 photons/MeV of absorbed X-ray energy for the samples Sr_1.86Ce_0.07Na_0.07Mg(BO₃)₂ and Sr_1.82Pr_0.09Na_0.09Mg(BO₃)₂ at RT, respectively.     

Luminescence of BaBr2:Eu under hydrostatic pressure

Luminescence spectra of BaBr₂:Eu²⁺ have been measured under pressures up to 27 GPa at room temperature. In the low-pressure range a red-shift of the 5d-4f transition of −225 cm⁻¹/GPa is observed. From 3 to 10 GPa a phase mixture of the original orthorhombic phase and the high-pressure monoclinic phase gives rise to two luminescence bands. Above 10 GPa the crystal is completely transformed to its high-pressure phase where two different Eu²⁺ sites exist of which, however, only one 5d-4f transition is detected. This transition exhibits a red-shift of −200 cm⁻¹/GPa. The shifts are compared with other literature data.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

Improved photoluminescence and afterglow in CaTiO3:Pr with addition of nanosized SiO2

Enhancement of the ¹D₂-³H₄ red emission in CaTiO₃:Pr³⁺ with addition of nanosized SiO₂ fabricated by a solid state reaction method is reported. The dynamical processes for the improvement of red emission were systematically investigated using photoluminescence (PL) and PL excitation spectra, and diffused reflectance spectra as well as time decay patterns of PL and persistent afterglow. Higher efficiency of energy transfer from CaTiO₃ host to the activator Pr³⁺ due to the improvement of crystallinity by SiO₂ addition was discussed in comparison with that of the SiO₂ free sample. The enhancement of persistent afterglow after the cessation of excitation in SiO₂ added CaTiO₃:Pr³⁺ was also analyzed by theoretically fitted results.     

Blue luminescence in Tm-doped KGd(WO4)2 single crystals

Up-conversion blue emissions of trivalent thulium ions in monoclinic KGd(WO₄)₂ single crystals at 454 and 479 nm are reported for a single pump laser source at 688 nm. We grew thulium-doped KGd(WO₄)₂ single crystals at several concentrations from 0.1% to 10%. We recorded a polarized optical absorption spectrum for the ³F₂+³F₃ energy levels of thulium at room temperature and low temperature (6 K). From the low temperature emission spectra we determined the splitting of the ³H₆ ground state. The blue emissions are characterized as a function of the dopant concentration and temperature from 10 K to room temperature. To our knowledge, this is the first time that sequential two-photon excitation process (STEP) generated blue emissions in thulium-doped single crystals with a single excitation wavelength.     

Photoluminescence properties of Sm-doped BaBr2 under hydrostatic pressure

Photoluminescence spectra of Sm²⁺-doped BaBr₂ have been measured under hydrostatic pressures up to 17 GPa at room temperature. In the low pressure range a red-shift of the broad 5d-4f transition of −145 cm⁻¹/GPa is observed. From 5 to 8 GPa a phase mixture of the initial orthorhombic phase and the high-pressure monoclinic phase gives rise to two 5d-4f bands, which are strongly overlapping. Above 8 GPa the crystal is completely transformed to its high-pressure phase where two different Sm²⁺ sites exist, but only one broad 5d-4f transition is detected. It exhibits a red-shift of −36 cm⁻¹/GPa. In addition, the line shifts of the ⁵D₀→⁷F_J (J=0, 1, 2) transitions are investigated. Linear shifts of −19 cm⁻¹/GPa for J=0, 2 and of −13 cm⁻¹/GPa for J=1 are observed in the pressure range from 0 to 5 GPa.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Study of the electron paramagnetic resonance spectra of Zn(antipyrine)2(NO3)2:VO

In this work, a full ligand-field energy matrix (10×10) diagonalization treatment for 3d¹ ions in tetragonal symmetry is developed on the basis of the two-s.o.-coupling-parameter model. Spin Hamiltonian parameters (g factors g_∥, g_⊥ and hyperfine structure constants A_∥, A_⊥) of the tetragonal V⁴⁺ center in Zn(antipyrine)₂(NO₃)₂ are calculated from the complete energy matrix diagonalization method and the perturbation theory method. The calculated results from both methods are not only close to each other but also in good agreement with the experimental values. Furthermore, the compressed defect structure of V⁴⁺ center is discussed.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Eu-activated Ba2Mg(BO3)2 yellow-emitting phosphors for near ultraviolet-based light-emitting diodes

A series of Eu²⁺-activated Ba₂Mg(BO₃)₂ yellow phosphors were prepared by a high temperature solid-state reaction. The phosphor emits intense yellow light under near ultraviolet excitation. Large Stokes shift can be attributed to the asymmetric nature of the Eu site and the lack of rigidity in the host. The concentration self-quenching mechanism of Ba₂Mg(BO₃)₂:Eu²⁺ is d-d interaction and the critical transfer distance is calculated to be about 12.29 Å. Prototype light-emitting diodes were fabricated by coating the Ba₂Mg(BO₃)₂:0.07Eu²⁺ phosphor onto ∼370 nm-emitting InGaN chips. The LEDs exhibit intense yellow-emitting under a forward bias of 20 mA. The results indicate that Eu²⁺-activated Ba₂Mg(BO₃)₂ is a candidate as a yellow component for fabrication of near-UV white light-emitting diodes.     

Crystal fields of Pr in LiYF4 under pressure

Fluorescence spectra of LiYF₄:Pr³⁺ have been measured between 12,000 and 22,000 cm⁻¹ under pressures up to 10 GPa. In total, 25 crystal field energy levels were obtained and used for the determination of free-ion and crystal field parameters under pressure. According to the nephelauxetic effect, the free-ion parameters decrease with increasing pressure. The relative decrease is larger for the Slater than for the spin-orbit coupling parameter. This behavior is consistent with former studies on Pr³⁺ in different crystals and can be explained by a special covalency model. According to an effective D_2d symmetry, five crystal field parameters B₀²(f,f), B₀⁴(f,f), B₄⁴(f,f), B₀⁶(f,f), and B₄⁶(f,f) are non-zero. The pressure-induced changes of these parameters have been determined up to the maximum pressure of 10 GPa. In order to improve the calculation of the crystal field levels, the configuration interactions with the 4f¹6p¹ configuration have been taken into account. The effect of these interactions are also analyzed under pressure and distinct improvements of the energy level calculations have been obtained.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Ionic liquid-assisted hydrothermal synthesis of dendrite-like NaY(MoO4)2:Tb phosphor

Micro-sized NaY(MoO₄)₂:Tb³⁺ phosphors with dendritic morphology was synthesized by a ionic liquid-assisted hydrothermal process. X-ray diffraction (XRD) indicated that the as-prepared product is pure tetragonal phase of NaY(MoO₄)₂. Field emission scanning electron microscopy (FE-SEM) images showed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors have dendritic morphology. The photoluminescent (PL) spectra displayed that the as-prepared NaY(MoO₄)₂:Tb³⁺ phosphors show a stronger green emission with main emission wavelength 545 nm corresponding to the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, and the optimal Tb³⁺ doping concentration for obtaining maximum emission intensity was confirmed to be 10 mol%. Based on Van Uitert's and Dexter's models the electric dipole–dipole (D–D) interaction was confirmed to be responsible for the concentration quenching of ⁵D₄ fluorescence of Tb³⁺ in the NaY(MoO₄)₂:Tb³⁺ phosphors. The intrinsic radiative transition lifetime of ⁵D₄ level is found to be 0.703 ms.     

Influence of high hydrostatic pressure on Eu-luminescence in KMgF3:Eu crystal

Spectroscopic investigations are presented of KMgF₃:Eu²⁺ crystal under high hydrostatic pressure from ambient to 310 kbar. The sample was excited by 30 ps pulses generated by optical parametric generator (OPG) system with wavelength controlled between 210 and 325 nm. The Grüneisen parameters of individual phonons are obtained from the pressure shift of the Eu²⁺ emission related to the ⁶P_7/2→⁸S_7/2 transition accompanied by phonon sideband. The luminescence decays exponentially for the pressure below 135 kbar with lifetime of 3.30 ms and slightly nonexponential above 135 kbar, while the average decay time is nearly independent of the pressure. The results obtained for KMgF₃:Eu²⁺ are compared with those for LiBaF₃:Eu²⁺ in which the ⁶P_7/2→⁸S_7/2 emission is replaced by the broadband emission of the 4f⁶5d¹→4f⁷ transition at high hydrostatic pressure.     

The influence of Pr co-doping on the luminescent properties of Lu2O3:5 mol% Eu films

Uniform and crack free polycrystalline lutetium oxide (Lu₂O₃:(Eu,Pr)) films were fabricated by Pechini sol-gel method combined with the spin-coating technique. X-ray diffraction (XRD) and atomic force microscope (AFM) characterizations indicated that the obtained film was composed of polycrystalline cubic Lu₂O₃ phase with an average grain size around 30 nm. The photoluminescence(PL) spectra and decay performances of the Lu₂O₃:5 mol% Eu films co-doped by 0-0.5 mol% Pr³⁺ with different concentrations were characterized. It was found that the afterglow was reduced obviously due to the introduction of 0-0.5 mol% Pr³⁺ in the Lu₂O₃:5 mol% Eu films coupled by decrease in the emission intensity at 612 nm. The mechanism of afterglow diminishing was discussed based on the thermoluminescence measurements.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.     

Excited states dynamics under high pressure in lanthanide-doped solids

Emission related to rare earth ions in solids takes place usually due to 4fⁿ→4fⁿ and 4fⁿ⁻¹5d¹→4fⁿ internal transitions. In the case of band to band excitation the effective energy transfer from the host to optically active impurity is required. Among other processes one of the possibilities is capturing of the electron at the excited state and the hole at the ground state of impurity.The latest results on high pressure investigations of luminescence related to Pr³⁺ and Eu²⁺ in different lattices are briefly reviewed. The influence of pressure on anomalous luminescence and 4fⁿ⁻¹5d¹→4fⁿ luminescence in BaSrF₂:Eu²⁺ and LiBaF₃:Eu²⁺ systems and Pr³⁺ 4fⁿ→4fⁿ emission quenching is presented and discussed. A theoretical model describing the impurity-trapped exciton as a system where a hole is localized at the impurity and an electron is captured by Coulomb potential at Rydberg-like states is developed. The results show the importance of local lattice relaxation for the creation of stable impurity-trapped exciton states. The ligands shifts create a potential barrier that controls the effect of mixing between the Rydberg-like electron and localized electron wave functions.     

Polarized fluorescence spectra analysis of Yb:KGd(WO4)2

The average fluorescence wavelength of the laser crystal is the most important factor in the radiation-balanced laser (RBL). Polarized fluorescence spectra measurements of the anisotropic laser material ytterbium-doped potassium gadolinium tungstate, Yb³⁺:KGd(WO₄)₂, are carried out along principal refractive index directions m, p, g in three configurations in order to achieve the best design for RBL. The average fluorescence wavelength of g polarization is the shortest, so g should be in the face of fluorescence emission; m polarization should be normal to that face to avoid its strong absorption to fluorescence photons. Fluorescence re-absorption causes the average fluorescence wavelength of the directly measured spectra red-shifted at least 9 nm. Methods for depressing radiation trapping are suggested accordingly, which are high power pumping, low doping concentration, small dimensions and fusing with undoped KGd(WO₄)₂.     

Group delay dispersion measurement of Yb:YAl3(BO3)4 crystal with white-light interferometry

We report the group delay dispersion of Yb³⁺:YAl₃(BO₃)₄ (Yb:YAB) crystal measured by a white-light interferometer, and compare with that calculated from the Sellmeier formulae provided by the crystal supplier, over the wavelength range from 1000 nm to 1080 nm. The data should be useful for the dispersion compensation for femtosecond pulse generation in Yb:YAB lasers.     

Growth and spectroscopic characterization of Er: Sr3Y(BO3)3 crystal

This paper reports the growth and spectroscopic characterization of Er³⁺:Sr₃Y(BO₃)₃ crystal. Er³⁺:Sr₃Y(BO₃)₃ crystal with dimensions up to ∅20×35 mm³ has been grown by Czochralski method. The polarized spectroscopic properties of Er³⁺:Sr₃Y(BO₃)₃ crystal were investigated. Based on the Judd-Ofelt theory, the effective intensity parameters Ω_t were obtained: Ω₂=1.71×10⁻²⁰ cm², Ω₄=1.39×10⁻²⁰ cm², Ω₆=0.74×10⁻²⁰ cm² for π-polarization, and Ω₂=1.77×10⁻²⁰ cm², Ω₄=1.44×10⁻²⁰ cm², Ω₆=0.65×10⁻²⁰ cm² for σ-polarization. The emission cross-section σ_em was calculated to be 4.75×10⁻²¹ cm² for π-polarization at 1536 nm and 6.30×10⁻²¹ cm² for σ-polarization at 1537 nm. The investigated results showed that Er³⁺:Sr₃Y(BO₃)₃ crystal may be regarded as a potential laser host material for 1.55 μm IR solid-state lasers.