Spectroscopic and laser properties of (Pr,La)P5O14 and (Pr,Y)P5O14 crystals

Systematic emission and absorption spectroscopic studies of Pr_xLa_1?xP₅O₁₄ (for x=1, 0.9, 0.8, 0.7, 0.5, 0.1) and Pr_xY_1?xP₅O₁₄ (for x=0.75 and 0.5) were performed at 300 and 77 K. The structure of Pr³⁺ energetic levels in pentaphosphates was determined for each concentration considered. Numerical values of the most important spectroscopic parameters — the emission cross section, fluorescence quantum yield and branching ratio — determining the laser properties of the compounds investigated, were evaluated. Also, the radiative lifetime and normalized quenching rate values were obtained. The results of the measurements complete the information about the laser properties of praseodymium pentaphosphates, which were reported in previous papers.     

Peculiarities of cascade photon emission and energy storage in M1−xPrxF2+x (M=Ca,Sr, Ba,x≈0.35) crystals

Peculiarities of cascade photon emission (CPE) and energy storage in M_1?xPr_xF_2+x (M=Ca, Sr, Ba, x≈0.35) crystals were studied. The investigation of lattice parameters revealed that these solid solutions belong to the fluorite structure type with the lattice constant noticeably different from that of MF₂ crystals. Absorption, emission and excitation spectra of M_0.65Pr_0.35F_2.35 were measured at LHeT and RT. As it turned out the typical for 4f²→4f² transition in Pr³⁺ emission lines are broadened as compared with the PrF₃ crystal. The analysis of the excitation spectra broadening does not allow bringing out the type of the superlattice, which is inherent to the material, but it indicates clearly the simultaneous presence of different types of the Pr centers in mixed crystals. Yet another specific feature is the higher radiation sensitivity of these fluorides relatively PrF₃, MF₂ and Pr-doped MF₂ crystals. Coloration efficiency enhances in direction Ca→Sr→Ba, and the positions of induced absorption band depend on composition of the solid solution. Colorization, thermo-stimulated luminescence and afterglow of the M_1?xPr_xF_2+x crystals denote high radiation sensitivity as compared with M_1?xCe_xF_2+x.     

Concentration-dependent fluorescence-quenching in La1−xPrxP5O14

The visible fluorescence of the Pr³⁺-ions in La_1?xPr_xP₅O₁₄ was investigated. The fluorescence starting from the level ³P₀ decays as a pure exponential with a time constant of 124 ns for all concentrations in the range of 4.2 K to 300 K, whereas the fluorescence of the level ¹D₂ shows a strongly concentration-dependent, nonexponential decay. The concentration-quenching arises from those ions which absorb in the wings of the inhomogeneous absorption lines, and can be attributed to Pr³⁺ pairs. We propose as a model of fluorescence-quenching the cross-relaxation between an excited Pr³⁺ ion and an adjacent ion in the ground state under emission of one phonon to the lattice. The frequently employed Inokuti-Hirayama continuum approximation fails when analyzing the time-resolved fluorescence of the a¹D₂ level. Only if the particular structure of the pentaphosphates is taken into account, it is possible to determine the dipole-quadrupole character of the Pr³⁺-Pr³⁺ interaction unambiguously.     

Luminescence properties of LiPrxCe1−xP4O12

LiPr_1−xCe_xP₄O₁₂ (x=0, 0.002, 0.02; 0.1) powder samples were prepared using the melt solution technique. Luminescent parameters of LiPr_1−xCe_xP₄O₁₂ phosphors have been investigated under ultraviolet-vacuum ultraviolet (3-12 eV) synchrotron radiation and X-rays excitation at room and near liquid He temperatures. Excitation luminescence spectra of Ce³⁺ emission, luminescent spectra and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configuration of the Pr³⁺ and Ce³⁺, respectively, clearly indicate energy transfer from Pr³⁺ to Ce³⁺. Energy migration proceeds via the Pr-sublattice followed by nonradiation transfer from Pr³⁺ to Ce³⁺ ions.     

Luminescent properties of trivalent praseodymium-doped lanthanum aluminum germanate LaAlGe2O7

The luminescent characteristics of Pr³⁺-activated LaAlGe₂O₇ were investigated. In response to excitement using 448 nm blue light, the emission spectra involved most of the ³P₀→³H_J transitions. The dominant emission came from the ³P₀→³H₄ transition at 487 nm. ¹D₂ fluorescence quenching was observed in highly doped samples and is related to the cross-relaxation processes among neighboring Pr³⁺ ions. In contrast with conventional Pr³⁺-activated phosphors, the extraordinary excitation spectra showed only intense f-f transition of Pr³⁺ ions, while the 4f-5d transition was eliminated. This is ascribed to photoionization. By analyzing absorption and excitation spectra, it is recognized that no efficient energy transfer occurs between Pr³⁺ and the host lattice in LaAlGe₂O₇.     

Broadening of the lines due to the 4f n -4f n − 15d transitions of Ce3+, Pr3+, and Tb3+ ions in the absorption spectra of CdF2 crystals

The structure of the absorption spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in the vicinity of 4f-5d transitions has been investigated. At low temperatures the absorption spectra exhibit a weakly pronounced fine structure, in contrast to narrow-line spectra in crystals of Ca, Sr, and Ba fluorides. The spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in CdF₂ can be considered as the absorption spectra of these ions in alkali-earth fluorides, broadened by 60–75 cm^?1. The broadening is related to the autoionization of electron from the local 5d(e _g ) level to the energy-degenerate states of the conduction band of CdF₂ crystal.     

Effects of compositional phase transitions on luminescence of Sr1−xCaxTiO3:Pr

The mixed-compound of Sr_1−xCa_xTiO₃ has shown several compositional phase transformations. Photoluminescence and excitation spectra of the samples with different x and doped with 0.2% Pr³⁺ were investigated. Changes in the emission spectra were observed in different phases. The blue emission at 491 nm from ³P₀ state was found quite strong in the tetragonal phase, and was thermally quenched in the orthorhombic phases. The intensity of the red luminescence from ¹D₂ increases with increasing content of calcium. The strongest red emission is obtained from CaTiO₃:Pr³⁺. The results are discussed based on the configuration coordinate model and interaction of Pr with the charge transfer exciton state of the Ti complex.     

Absorption and emission spectra of yttria-stabilized zirconia and magnesium oxide

We have investigated the luminescence and absorption spectra of doped and undoped ZrO₂-Y₂O₃ and MgO crystals at room- and low temperatures. The crystals used are partly doped with the transition metals Ni, Co, Cr and the rare earth Pr. The emission spectra were obtained under laser excitation at different wavelengths. The observed optical emission and absorption bands of the MgO crystals doped with Ni, Co and Cr correspond to transitions between spin-orbit split crystal field levels of the transition metals. Luminescence and absorption bands of undoped yttria-stabilized zirconia (YSZ) crystals are due to color centers, absorption bands of the doped YSZ correspond to the well known transitions of the Ni²⁺, Co²⁺ and Pr³⁺ ions, respectively. The emission spectra of the doped YSZ obtained under various laser excitations can be explained by an energy transfer process between the color center and the doping materials. The influence of annealing on the absorption and emission of Pr³⁺/Pr⁴⁺ is investigated.     

Effect of interface states associated with transitional nanophase precipitates in the enhancement of red emission from SrAl12O19:Pr by Ti incorporation

SrAl₁₂O₁₉:Pr³⁺, Ti⁴⁺ phosphor suitable for field emission displays is prepared by the wet chemical gel-carbonate method and the mechanism of enhancement in red photoluminescence (PL) intensity with Ti⁴⁺ therein has been investigated. The PL spectra of Pr³⁺ show both ¹D₂-³H₄ and ³P₀-³H₆ emission in the red region with very weak intensity when excited at 355 nm. The emission intensity has increased by about 100 times at room temperature in the compositional range SrAl_12−xTi_xO_19+x/2:Pr³⁺, with 0.1≤x≤0.3 in comparison to Ti-free SrAl₁₂O₁₉:Pr³⁺. TEM investigations show the presence of exsolved nanophase of SrAl₈Ti₃O₁₉, the precipitation of which is preceded by the presence of defect centers at the interfacial regions between the semicoherent transient phase and the parent SrAl₁₂O₁₉ matrix. The presence of transitional nanophase and the associated defects modify the excitation-emission process by way of formation of electronic sub-levels at lower energy (3.5 eV) than the band gap of SrAl₁₂O₁₉ (∼7 eV) followed by non-resonance energy transfer to Pr³⁺ level, leading to magnetic-dipole related red emission with enhanced intensity. The PL intensity of Pr³⁺ decreases at high Ti⁴⁺ concentrations (x>0.3) due to higher extent of segregation of non-emissive SrAl₈Ti₃O₁₉:Pr³⁺ phase.     

Optical absorption and emission properties of Pr and Er in lithium cesium mixed alkali borate glasses

This article presents the optical absorption and emission properties of Pr³⁺ and Er³⁺ in mixed alkali borate glasses of the type 68B₂O₃·xLi₂O·(32-x)Cs₂O (where x=8, 12, 16, 20 and 24). The variation of Judd-Ofelt intensity parameters (Ω_λ), the peak wavelength of the hypersensitive transitions, radiative transition probabilities (A_rad) and peak emission cross-sections (σ_p) with x in the glass matrix have been discussed in detail. The changes in position of hypersensitive transition and intensity parameters with x are correlated to the structural changes in the host matrix. The estimated radiative lifetimes (τ_R) of certain excited states of both Pr³⁺ and Er³⁺ in lithium cesium mixed alkali borate glasses are reported. Branching ratios (β) and integrated absorption cross-sections (Σ) for certain important transitions are presented. Peak stimulated emission cross-sections (σ_p) are calculated for the observed emission peaks of Pr³⁺ and Er³⁺ ions in this glass matrix.     

Emission characteristics of Dy3+ ions in lead antimony borate glasses

Glasses with the composition 30PbO–25Sb₂O₃–(45?x)B₂O₃–xDy₂O₃ for x=0 to 1 were prepared in steps of 0.2 by the melt-quenching method. Various physical parameters, viz., density, molar volume, and oxygen packing density, were evaluated. Optical absorption and luminescence spectra of all the glasses were recorded at room temperature. From the observed absorption edges optical band gap, the Urbach energies are calculated; the optical band gap is found to decrease with the concentration of Dy₂O₃. The Judd–Ofelt theory was applied to characterize the absorption and luminescence spectra of Dy³⁺ ions in these glasses. Following the luminescence spectra, various radiative properties, like transition probability A, branching ratio β and the radiative life time τ for different emission levels of Dy³⁺ ions, have been evaluated. The radiative lifetime for the ⁴F_9/2 multiplet has also been evaluated from the recorded life time decay curves, and the quantum efficiencies were estimated for all the glasses. The quantum efficiency is found to increase with the concentration of Dy₂O₃.     

Laser induced emission spectra of Pr3+ in CaF2 at low temperatures

The luminescence spectra of Pr³⁺ in CaF₂, excited with the 4765.05 Å line of the argon ion laser at low temperatures, consist of many more emission lines than the maximum allowed via the ³P₀→³H_4,5,6; ³F_2,3,4 transitions of a single Pr³⁺-site. Based upon their intensity, appropriate splittings and concentration dependence, these emission lines are divided into three groups, attributed to different sites of Pr³⁺ in CaF₂. The existence of Pr³⁺ ions in defect sites of different symmetries is supported by theoretical calculations. The laser emission spectra of Pr³⁺ at low temperatures are compared with room temperature emission spectra obtained with excitation of the ³P₀ state alone, and with low temperature spectra of Pr³⁺ in different hosts, reported in the literature.     

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     

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.     

Investigation of gain characteristics in mixed crystals LiMeF4 (Me = Y,Lu, Yb) doped by Ce3+ ions

Differential gain spectra in the range 295–335 nm were measured in crystals of scheelite structure LiY_{1 ? x} Lu _x F₄ (x = 0–1), doped by Ce³⁺ ions. It is shown that variation of Lu³⁺ and Y³⁺ ions relative content in LiY_{1 ? x} Lu _x F₄ crystals allows to manipulate the spectral width of the amplification band. Cross-sections of excited-state absorption at the wavelengths of Ce³⁺ luminescence, probability ratios of formation and thermal destruction of color centers depending on the Y³⁺ ions content in LiY_{1 ? x} Lu _x F₄ crystals were estimated. Even better gain characteristics have been demonstrated by LiLuF₄:Ce³⁺, doped by Yb³⁺ ions. The highest optical gain coefficient with a wide amplification band among studied samples was observed in LiLuF₄:Ce³⁺ crystal, codoped by Yb³⁺ ions.     

XAFS studies of the local structure and charge state of the Pr impurity in SrTiO3

Solid solutions of (Sr_{1 ? x} Pr _x )TiO₃ have been studied using X-ray methods. It has been shown that, with an increase in the praseodymium concentration, the temperature of the structural phase transition to the phase with space group I4/mcm increases and, at x ?? 0.15, the structure at 300 K is tetragonal. X-ray absorption fine structure (XAFS) spectroscopy studies have revealed that Pr ions are predominantly in the charge state 3+ and occupy the Sr sites. No indications of the off-centering of Pr atoms at the Sr sites have been revealed. The local environment of Pr atoms is characterized by a strong relaxation of the oxygen atoms, the value of which corresponds to the difference between the ionic radii of Pr³⁺ and Sr²⁺. It has been found that, in the second shell, there occurs a significant repulsion of the Pr³⁺ and Ti⁴⁺ ions, which is responsible for the weak dependence of the lattice parameter in the solid solution on the praseodymium concentration.     

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.     

Fluorescence of Pr3+-ions in La1−xPrxP5O14

The fluorescence spectrum of La_1?xPr_xP₅O₁₄ was investigated for the range of 0.001 ? x ? 1. For small Pr³⁺-concentration the fluorescence starts almost completely from the ¹D₂ level, whereas in pure PrUP the total fluorescence arises from the energetically higher ³P₀ level. This is contrary to the usually observed concentration quenching. In the intermediate concentration range fluorescence lines from both levels are observed independent of the excitation.     

Role of Al coordination in barium phosphate glasses on the emission features of Ho ion in the visible and IR spectral ranges

The glasses of the composition (39−x)BaO-xAl₂O₃-60P₂O₅:1.0Ho₂O₃ (in mol%) with x value ranging from 1.0 to 4.0 have been synthesized. The IR spectral studies of these glasses have indicated that there is a gradual transformation of Al³⁺ ions from tetrahedral to octahedral with increase in the concentration of Al₂O₃ up to 3.0 mol%. Optical absorption and fluorescence spectra (in the visible and NIR regions) of these glasses have been recorded at room temperature. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of Ho³⁺ ions in these glasses. From the luminescence spectra, various radiative properties like transition probability A, branching ratio β_r, the radiative lifetime τ_r and emission cross-section σ^E for various emission levels of these glasses have been evaluated. The radiative lifetime of the ⁵S₂→⁵I₈ (green emission) transition has also been measured. The variations observed in these parameters have been discussed in the light of varying co-ordinations (tetrahedral and octahedral positions) of Al³⁺ ions in the glass network. The influence of hydroxyl groups on the luminescence efficiency of the transition ⁵S₂→⁵I₈ has also been discussed. Finally the optimum concentration of Al₂O₃ for getting maximum luminescence output has also been identified and reported.