The 1S0 emission from the minor site of Pr3+ in (Ba,La)F2:Pr

In this paper we present and discuss results of detailed spectroscopy studies of Pr³⁺ luminescence from the (Ba,La)F₂:0.2 m%Pr crystals under UV and VUV synchrotron excitation.We have measured time resolved emissions from the minor site Pr³⁺ in (Ba,La)F₂:Pr at 10 and 300 K. The spectra clearly show the ¹S₀ emission from the Pr³⁺ ions in some low symmetry Pr-sites (we designate them La-sites) previously identified in higher concentration (0.3 m%Pr and more) crystals. However most of emission from the Pr activated (Ba,La)F₂ crystals originates in Pr³⁺ ions in other sites which produce an efficient d-f emission. As demonstrated by excitation spectra, the emission from some of these sites (denoted as Ba-sites) closely resembles the d-f emission from BaF₂.The La-site, time resolved and long delay emission spectra are dominated by hypersensitive transitions from the ¹S₀ and ³P₀ levels to lower energy levels of the 4f² configurations. Only these transitions contribute to the photon cascade emission desired for some mercury free phosphor applications.     

Emission spectroscopy and ionic interaction in K5PrLi2F10

Emission spectroscopy of Pr³⁺ in a newly discovered compound, K₅PrLi₂F₁₀, is presented. An energy level diagram of Pr³⁺ in this lattice is given. Dilution with Gd and La shows that concentration quenching caused by Pr-Pr interaction takes place. Dilution with Ce shows, in addition, a strong Pr-Ce interaction resulting in non-radiative ³P₀-¹D₂ conversion occurring in competition with direct ³P₀ to ground state decay. Analysis based on a statistical model is not able to distinguish between Pr interaction with Ce singles or pairs, but it leads to different conclusions than reached for Pr : LaF₃.     

Fundamental aspects of activated nanocrystal luminescence and possible applications

Presented results of complex study of relaxation processes and interionic interaction in Y₂SiO₅:Pr³⁺ and Lu₂SiO₅:Ce³⁺ nanocrystals clearly show two fundamental aspects: the phonon quantum confinement gives rise to the new fluorescence dynamics of doped ions; the developed surface of nanocrystals stimulates the irregular distribution of doped ions within the nanocrystal volume and could be the reason of new atomic arrangement of nanocrystal. Fluorescence spectrum of isolated Y₂SiO₅:Pr³⁺nanocrystal demonstrates the intense fluorescence from the high crystal field components of split ¹D₂ manifold of Pr³⁺ as the result of a suppression of phonon-assisted relaxation under the phonon quantum confinement. The direct comparison of the data obtained for nano- and bulk Y₂SiO₅:Pr³⁺ crystals has revealed that the concentration threshold of luminescence quenching is strikingly low for nanocrystals. This effect is caused by uphill diffusion of doped ions and preferred Pr segregation at the nanocrystal surface layer that provides the relaxation of elastic tension arising due to the difference of ionic radii of Pr³⁺ and Y³⁺. Lu₂SiO₅:Ce³⁺ nanocrystals which average size is 5 nm do not demonstrate the effect of energy storage as the result of atomic packing changing that does not permit the existence of electronic traps.     

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.     

Temperature dependence of 3P0 Pr3+ fluorescence dynamics in Y4Al2O9 crystals

Temperature-dependent emission spectra and fluorescence dynamics profiles have been investigated in Pr³⁺:Y₄Al₂O₉ crystals in order to better understand the processes responsible for quenching of the praseodymium ³P₀ emissions. The cross-relaxation transfer rates were experimentally determined as a function of temperature. Using the rate equations formalism, the dynamics of the observed emissions were modeled. Basing on comparison between the measured and calculated decays, the energy transfer rates between Pr³⁺ ions were evaluated. The role of the backward process in explanation of the complicated character of ³P₀ decays and its temperature dependence, especially its unexpectedly slow decaying component, were established.     

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 of Ca(NbO3)2:Pr at ambient and high hydrostatic pressure

In this contribution, photoluminescence and time-resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺ obtained at high hydrostatic pressure up to 72 kbar applied in a diamond anvil cell are presented. At ambient conditions, the emission spectrum obtained in the time interval 0-1 μs is dominated by spin-allowed transitions from the ³P₀ state. On the other hand, transitions from ¹D₂, characterized by a decay time equal to 30 μs dominate the steady-state luminescence.At pressures lower than 60 kbar, the continuous wave emission spectrum consists of sharp lines peaking between 600 and 625 nm, related to the ¹D₂→³H₄ transition and three lines at 500, 550 and 650 nm related to emission transitions originating from the ³P₀ level of Pr³⁺. The emission from the ¹D₂ excited state depends weakly on the pressure. Its decay time decreases from 33 μs at ambient pressure to less than 22 μs at 68 kbar. On the other hand, the ³P₀ emission is strongly pressure dependent. At pressures of 60 kbar and higher, the Pr³⁺ emission intensity from the ³P₀ state decreases. This is accompanied by a strong shortening of the luminescence decay time.The observed pressure quenching of the f-f emission transitions and the concomitant lifetime shortening have been attributed to increasing crossover from the ³P₀ state of Pr³⁺ to a Pr³⁺-trapped exciton state.     

Quenching of Lanthanide Emission by Intervalence Charge Transfer in Crystals Containing Closed Shell Transition Metal Ions

The quenching of the luminescence originating from the excited states ³P₀ and ¹D₂ of Pr³⁺ and ⁵D₃ and ⁵D₄ of Tb³⁺ has been studied in oxide crystals containing closed shell transition metal ions, such as titanates, vanadates, niobates, and tantalates. It has been shown that the emission from these excited states can be quenched by an intervalence charge transfer mechanism. The temperature dependence of the emission intensities has allowed estimating indicative activation energies for the crossover to the intervalence charge transfer state. In the case of Tb³⁺, the quenching gives rise to relatively short decay times for the ⁵D₄ state.     

Anomalies in the concentration quenching of luminescence in doped Y2SiO5:Pr3+ nanocrystals

In Y₂SiO₅:Pr³⁺ nanocrystals, an ordered phase is observed in the ¹ D ₂ luminescence decay curves of Pr³⁺ ions at their anomalously low concentration (0.5 at %). This effect is caused by the predominant accumulation of activator ions near the nanocrystal surface, which provides relaxation of the elastic strains arising as a result of the misfit between the ionic radii of Pr³⁺ and Y³⁺. The concentration quenching of Pr³⁺ luminescence is due to cooperative cross relaxation.     

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.     

Spectral-kinetic characteristics of Pr luminescence in LiLuF4 host upon excitation in the UV-VUV range

Spectral-kinetic study of Pr³⁺ luminescence has been performed for LiLuF₄:Pr(0.1 mol%) single crystal upon the excitation within 5-12 eV range at T=8 K. The fine-structure of Pr³⁺ 4f ²→4f 5d excitation spectra is shown for LiLuF₄:Pr(0.1 mol%) to be affected by the efficient absorption transitions of Pr³⁺ ions into 4f 5d involving 4f ¹ core in the ground state. Favourable conditions have been revealed in LiLuF₄:Pr(0.1 mol%) for the transformation of UV-VUV excitation quanta into the visible range. Lightly doped LiLuF₄:Pr crystals are considered as the promising luminescent materials possessing the efficient Pr³⁺³P₀ visible emission upon UV-VUV excitation. The mechanism of energy transfer between Lu³⁺ host ion and Pr³⁺ impurity is discussed.     

Pr3+在SBN晶体中的发光特性

通过测量Ｐｒ：ＳＢＮ晶体的吸收光谱和荧光光谱来确定Ｐｒ³⁺在ＳＢＮ晶体中的能级位置。由于Ｐｒ³⁺离子占据晶体中的不同格位而引起荧光带呈现双峰结构。测量荧光寿命随温度的变化关系，表明Ｐｒ³⁺在ＳＢＮ晶体中 ³Ｐ₀态的无辐射弛豫主要是 ³Ｐ₀→¹Ｄ₂多声子弛豫过程。 关键词：     

Concentration quenching anomalies of activated Y<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Pr<Superscript>3+</Superscript> nanocrystal luminescence

For the fist time in Y₂SiO₅:Pr³⁺ nanocrystals, the ordered stage in the ¹ D ₂ luminescence decay curves for Pr³⁺ ions has been observed at anomalously low doped ion concentration (0.5 at %). This effect is caused by preferred location of the activator ions in the near-surface layer of the nanocrystal that provides the relaxation of elastic tension arising due to the difference of ionic radii of Pr³⁺ and Y³⁺ ions. Concentration quenching of Pr³⁺ luminescence is caused by the cooperative cross-relaxation.     

A cross-relaxation mechanism of fluorescence quenching in complexes of lanthanide ions with organic ligands

For the first time, direct experimental evidence of a new mechanism for the quenching of fluorescence of organic ligands (L) in complex compounds with lanthanide ions (Ln³⁺) is obtained. By analogy with the mechanism of luminescence quenching upon pair interactions of Ln³⁺ ions in inorganic systems, this mechanism is called the cross-relaxation mechanism. The experiments are performed with complexes of Tb³⁺ with dianions of halogen-substituted fluoresceins (HSFs): 4,5-dibromo-and 4,5-diiodofluorescein, eosin B, eosin, erythrosin, and Rose Bengal in dimethyl sulfoxide. In accordance with this mechanism—exchange energy transfer, L^2?(*S ₁), Tb³⁺(⁷ F ₆)→L^2?(T ₁), Tb³⁺(⁷ F _{5, 4}), allowed by the spin selection rules—an increase in the quantum yield of formation of the triplet state (Φ_T) of a ligand L^2? and a decrease in the quantum yield of fluorescence (Φ_fl) are found to take place upon complexation. The efficiency of this process amounts to ～1 in accordance with the equality Φ_fl+Φ_T=1, valid for solutions of HSFs. The possibility of other processes leading to a similar effect, specifically, recharging of the system (as for complexes of HSFs with Eu³⁺ and ³⁺) is considered. An example of inductive resonance interactions in complexes of HSFs with Pr³⁺ is given. The manifestation of equilibrium between outer-sphere and inner-sphere complexes in the photophysics of complexes of metals with HSFs is discussed.

     

Affinement d'une raie de fluorescence de Pr3+: LaAlO3 par excitation laser

A cw dye laser has been used for fluorescence line narrowing experiments by resonant excitation on Pr³⁺ ions in LaAlO₃. Scanning the excitation radiation through the absorption line width corresponding to the transition ³H₄ (0 cm^-1) → ¹D₂ (16 694 cm^-1) while fluorescence was observed, has put into evidence a deformation of the symmetry around Pr³⁺ ions, different for every site.This experiment shows the power of cw dye laser spectroscopy for investigating optical spectra in crystals.     

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.     

Luminescence of CaWO4:Pr3+ and CaWO4:Tb3+ at ambient and high hydrostatic pressures

Photoluminescence spectra of CaWO₄ doped with Pr³⁺ and Tb³⁺ obtained at high hydrostatic pressures up to 315 kbar applied in a diamond anvil cell (DAC) are presented. The intensities of the luminescence from the ³P₀ state of Pr³⁺ and from the ⁵D₃ state of Tb³⁺ decreased with increasing pressure. At pressures greater than 50 kbar, the ¹D₂ → ³H_J transitions in Pr³⁺ and the ⁵D₄ → ⁷F_J transitions in Tb³⁺ dominated the spectra. At pressures greater than 100 kbar, only emissions from the lower excited states were observed. At pressures greater than 150 kbar, luminescence from the ¹D₂ and ⁵D₄ states also decreased with increasing pressure, and at a pressure of 315 kbar for CaWO₄:Pr³⁺ and 190 kbar for CaWO₄:Tb³⁺, the emissions related to the Pr³⁺ and Tb³⁺ were quenched. These effects were related to the influence of impurity trapped excitons (ITEs) on the efficiency of the f–f emission in the Pr³⁺ and Tb³⁺ ions. Analysis of the emission spectra collected at different pressures allowed the energies of the ground states of the Pr³⁺ and Tb³⁺ ions with respect to the band edges of the CaWO₄ host to be estimated.     

Optical absorption, fluorescence and decay properties of Pr-doped PbO-H3BO3-TiO2-AlF3 glasses

Spectroscopic and laser properties of PbO-H₃BO₃-TiO₂-AlF₃ glasses doped with 0.1, 0.5, 1.0 and 2.0 mol% of Pr₆O₁₁ have been studied. Optical absorption spectra were recorded in the UV-vis-NIR regions and the observed absorption bands were assigned to different electronic transitions from ³H₄ ground state of 4f² configuration. The three phenomenological Judd-Ofelt (J-O) parameters Ω_t (t=2, 4, 6) were determined from the measured oscillator strengths by including as well as excluding the ³H₄→³P₂ hypersensitive transition in J-O analysis. The emission characteristics such as stimulated emission cross-sections (σ_e), measured branching ratios (β_m), measured lifetimes (τ_m), quantum efficiencies (η) and gain parameters (σ_e×τ_m) have been evaluated for the principal intermanifold transitions of Pr³⁺ from the ³P₀ and ¹D₂ states to the lower lying manifolds in the visible region. From the emission and decay measurements, the effect of Pr³⁺ ion concentration on the quenching of the ¹D₂ measured lifetimes has been discussed.     

Dynamic quenching of the multiband fluorescence of 3-hydroxyflavone

The properties of emission, absorption, and dual fluorescence excitation of 3-hydroxyflavone in acetonitrile are studied under the conditions of dynamic quenching by potassium iodide with concentrations up to 4 × 10^?2 M. The normal and tautomeric forms undergo quenching, which is more efficient for the tautomeric form. An interesting circumstance is that the absorption in the S ₀ → S ₁ and S ₀ → S ₂ singlet bands of the solution increases with increasing quencher concentration in the whole region of concentrations used, the steepest rise being recorded in the concentration region from 0 to 5 × 10^?3 M. The intensities and quantum yields of the two fluorescence bands show rather complicated nonlinear dependences on the quencher concentration. The long-wavelength fluorescence band, which belongs to the tautomeric form of 3-hydroxyflavone, is quenched considerably stronger. The experimental results reveal the kinetic character of the excited-state proton transfer in molecules of 3-hydroxyflavone in acetonitrile.