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.     

Echo spectroscopy of two-level systems in a Y2SiO5: Pr3+ crystal

The results of an experimental investigation of low-temperature optical spectra and phase relaxation of electronic excitations of Pr³⁺ impurity ions in a Y₂SiO₅ crystal are reported. It is established that at low temperatures spectral lines are broadened by a mechanism that is uncharacteristic for crystals and is due to the interaction of impurity ions with two-level systems. The constants characterizing the interaction of Pr³⁺ impurity ions with phonons and two-level systems are found. Zh. éksp. Teor. Fiz. 115, 704–715 (February 1999)     

The nature of activation centers in Y2SiO5:Pr3+, Gd2SiO5:Pr3+, and Lu2SiO5:Pr3+ crystals

A complex study of the energy spectra and relaxation channels for the excitation energy of activation centers in Y₂SiO₅:Pr³⁺, Lu₂SiO₅:Pr³⁺, and Gd₂SiO₅:Pr³⁺ was performed. An analysis of the low-temperature optical spectra showed that the energy parameters and the character of field splitting of the ¹ D ₂ and ³ H ₄ activator ion terms were substantially different in crystals of different crystallographic types. The pseudosymmetry effect was observed in splitting of the ¹ D ₂ and ³ H ₄ terms of Pr³⁺ ions situated in nonequivalent crystal lattice cation sites of Y₂SiO₅ and Lu₂SiO₅. Activator ions nonuniformly populated nonequivalent cation sites of the Y₂SiO₅ crystal lattice. At high activator ion concentrations (>1 at %), luminescence decay in Y₂SiO₅ could not be described by a simple exponential time dependence. The complex luminescence decay law was caused by activator ion excitation energy migration and capture by acceptors. The role of energy acceptors was played by activator ion dimers.     

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.     

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.     

Strong segregation of doped ions in Y2SiO5:Pr3+ nanocrystals

Strong temperature controlled segregation of doped ions in Y₂SiO₅:Pr³⁺ nanocrystals detected by spectroscopic techniques is reported. The elastic interactions stimulate Pr³⁺ segregation thus leading to non-uniform distribution of doped ions, pair formation and, as a consequence, to abnormal low threshold of luminescence concentration quenching for Y₂SiO₅:Pr³⁺ nanocrystals.     

Laser excitation of Pr3+ sites in ThCl4:Pr3+

Use of site selection spectroscopic techniques combined with low temperature absorption spectral studies has enabled the identification and characterization of ten optically important charge-compensated crystallographic sites for Pr³⁺ in the β-ThCl₄:Pr³⁺ system. Fluorescence decay time measurements, variation of site distribution with dopant concentration and fluorescence spectra were used to characterize the sites. Distant charge compensation is found to be one of the dominant modes of charge compensation of Pr³⁺ in ThCl₄, and its predominance over other sites increases as Pr³⁺ concentration decreases. The sinusoidal distortion of the crystal field symmetry around Pr³⁺ in the incommensurate phase of β-ThCl₄ is believed to be mainly responsible for the splitting and continuous shift in fluorescence spectral lines which occur when ³P₀→³F₂ fluorescence scans are made with excitation at different points on the ³P₀←³H₄ absorption line belonging to different sites.     

Luminescence of Ca(NbO3)2:Pr3+: Pr3+ and self-trapped exciton emission

Photoluminescence and time resolved photoluminescence spectra of Ca(NbO₃)₂ doped with Pr³⁺, excited under 37,000 cm^?1 (270 nm), obtained at high hydrostatic pressure up to 20 kbar applied in a sapphire anvil cells, 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. The luminescence related to transitions from ¹D₂, characterized by a decay time equal to 33 μs, is observed when one excites directly the Pr³⁺ ion with 30,770 cm^?1 (325 nm) wavelength. The introduction of Pr³⁺ impurities in Ca(NbO₃)₂ does not quench the self-trapped exciton (STE) luminescence. This luminescence, peaking at 20,000 cm^?1 (500 nm), having a decay time of 61 ± 1 μs, still occurs when the crystal is excited with a wavelength of 37,000 cm^?1 (270 nm) or shorter. Under such excitation a fraction of the STE luminescence is reabsorbed by Pr³⁺ ions; in this case the emission lifetime of the ¹D₂ → ³H₄ transition of Pr³⁺ is 64 ± 3 μs. This effect is stable also at high pressure.     

Photon echo “decay” in LaF3 : Pr3+ as a modulation process

The variation of photon echo intensity in LaF₃ : Pr³⁺ measured as a function of pulse separation for short times is shown to be a consequence of echo modulation as caused by isolated non-interacting Pr³⁺ ions.     

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     

Strong quenching of praseodymium f-f luminescence induced by a surface of Y2SiO5:Pr nanocrystal

The direct comparison of the luminescence decay data obtained for nano- and bulk Y₂SiO₅:Pr³⁺ crystals has revealed that the concentration threshold of luminescence quenching is strikingly low for nanocrystals. Nanocrystal inhomogeneous stress field induced by a surface stimulates the segregation of the doped Pr³⁺ ions within the surface layer that provides the relaxation of elastic tension arising due to the difference of the ionic radii of Pr³⁺ and Y³⁺. The Pr³⁺ irregular distribution in the nanocrystal volume results in the Pr³⁺ local concentration increasing that facilitates the luminescence quenching.     

Optical transitions of Pr3+ and Er3+ ions in LiYF4

The optical absorption, emission, and excitation spectra of Pr³⁺ and Er³⁺ ions in LiYF₄ have been measured and energy level schemes established which agree with previous work. The temperature dependence of the emission lifetimes were investigated and analyzed using the Huang-Rhys and Struck-Fonger treatments of multiphonon decay. The non-radiative processes in LiYF₄: Er³⁺ were shown to follow the same “gap law” behavior as Er³⁺ in LaF₃ and MnF₂. Theoretical fits to the Huang-Rhys model allowed the construction of a configuration coordinate diagram for the Er³⁺ system. The non-exponential temperature dependence of the ¹D₂ lifetime in Pr³⁺ can be understood as a non-radiative transition from higher levels.     

Optical spectra and luminescence dynamics of Pr3+ and Nd3+ in SrLaAlO4 single crystals

Single crystals of SrLaAlO₄: Pr³⁺ and SrLaAlO₄: Nd³⁺ have been grown by the Czochralski method and their optical properties have been studied for different activator concentrations. The absorption and emission spectra of the activators are inhomogeneously broadened because the Sr²⁺ and La³⁺ ions are distributed randomly on the sites ofC ₄ symmetry, however, the symmetry selection rules are still obeyed. Strong self-quenching of the praseodymium luminescence occurs by cross relaxation which is supposed to be assisted by phonon emission in the case of the³ P ₀ level. Self-quenching of Nd³⁺ luminescence disappears at low temperature indicating that the condition of resonance in the cross-relaxation process is fulfilled only for higher components of the ground state.Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw, Poland     

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.     

The laser-diode-excited 5d-4f luminescence of Ce3+ and Pr3+ ions embedded into a BaR2F8 matrix

We show the possibility of obtaining UV luminescence from 5d-4f transitions of rare-earth ions in the BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) crystal under upconversion excitation by standard laser diodes with lasing wavelengths of 960, 808, and 840 nm. Various upconversion mechanisms of pumping for populating the higher-lying energy levels of the active ions, as well as methods of adaptation of the active medium BaY₂F₈: (Yb³⁺, Pr³⁺, Ce³⁺) to these mechanisms, are considered.     

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.     

Luminescence of Cs2NaScCl6:Pr3+: Effects of Changing the Elpasolite Lattice Parameter

Abstract

The luminescence spectrum of Cs₂NaScCl₆:Pr³⁺ (0.1 at.%) has been recorded at temperatures down to 10 K and assigned between 20,800 and 9900 cm^?1. Twenty‐three energy levels of the 4f² configuration Pr³⁺ ion were located and then fitted by the conventional 4f² crystal field calculation, as well as by a configuration interaction assisted crystal field (CIACF) calculation. The latter gave a much better fit. A comparison of the fit for Cs₂NaScCl₆:Pr³⁺ with fits upon the same set of energy levels in Cs₂NaYCl₆:Pr³⁺ and Cs₂NaPrCl₆, where the fifth nearest neighbor of Pr³⁺ is changed and the lattice parameter increases along this series, shows a decrease in the magnitudes of the crystal field parameters, which were also semiquantitatively simulated. Several facets of the emission spectra are interesting, including the observation of weak progressions in the totally symmetric Pr–Cl stretching vibration and the occurrences of the resonance of electronic and vibronic states. The spectra of Cs₂NaScCl₆:Pr³⁺ (1 at.%) differ considerably from those of the more dilute system and show that other species are formed rather than a complete substitution of the Sc³⁺ sites by Pr³⁺.     

Luminescence characteristics of the Pr3+ ion in SrAlF5

The paper reports on a study of luminescence and excitation spectra of SrAlF₅:Pr³⁺ (0.5 mol %) polycrystals performed at 10 and 300 K with synchrotron radiation in the range from 5 to 25 eV. The Pr³⁺ ions in SrAlF₅ were shown to emit successively two photons in transitions from the ¹ S ₀ and ³ P ₀ levels. The main energy characteristics of the compound, namely, the position of the 4f → 5d excitation band (5.95–8.0 eV), the energy separation between the ¹ S ₀, 4f and the lowest 5d levels (～0.15 eV), and the SrAlF₅ band gap width (～12 eV), were determined. SrAlF₅:Pr³⁺ was found to possess a number of features not found in other Pr³⁺-activated fluorides.     

Up-conversion multiwave (White) luminescence in the visible spectral range under excitation by IR laser diodes in the active BaY2F8:Yb3+,Pr3+ medium

The possibilities of occupying high-lying 4f states of Pr³⁺ ions in the active BaY₂F₈:Yb³⁺,Pr³⁺ medium according to the photon avalanche and step-by-step sensitization mechanisms are compared. It is shown that the photon avalanche is unlikely to occur in the BaY₂F₈:Yb³⁺,Pr³⁺ crystal. The multiband luminescence spectra in the visible spectral range (white emission) under single- and multiwave pumping of BaY₂F₈:Yb³⁺,Pr³⁺ crystal by IR laser diodes are reported.