Formation of Eu<Superscript>2+</Superscript> and Eu<Superscript>3+</Superscript> centers in synthesis of CaF<Subscript>2</Subscript>:Eu luminophores

We have studied the effect of CaF₂:Eu luminophore synthesis methods on the charge state of europium. We have shown that Eu³⁺ predominates over Eu²⁺ in samples obtained by coprecipitation of europium with calcium fluoride, and the ratio Eu³⁺/Eu²⁺ grows as the total amount of europium increases. Partial charge conversion of the europium occurs during calcination of the samples, due to changes in the excess fluorine balance. We studied the luminescence, magnetic susceptibility, and EPR of the synthesized samples. We have shown that in a solid solution, europium forms large ordered clusters, determining both the luminescent and the magnetic properties of the material. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 773–779, November–December, 2007.     

Local structure of Gd<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> impurity centers in a CdF<Subscript>2</Subscript> crystal

The local crystal structure of Gd³⁺ and Eu²⁺ cubic impurity centers in cadmium fluoride is calculated within the shell model in the pair potential approximation. The local compressibility of the cationic and anionic sublattices of the host lattice is determined in the vicinity of the Gd³⁺ (Eu²⁺) impurity ion.     

EPR and optical spectroscopy of Yb<Superscript>3+</Superscript> ions in CaF<Subscript>2</Subscript>: an analysis of the structure of tetragonal centers

CaF₂ crystals doped with Yb³⁺ ions have been studied by electron paramagnetic resonance (EPR) and optical spectroscopy. EPR spectra of paramagnetic centers (PCs) for cubic (T_c) and tetragonal (T_tet) symmetries were identified. Empirical energy level diagrams were established and crystal field parameters were determined. Information on the CaF₂∶Yb³⁺ phonon spectra was obtained from the electron-vibrational structure of the optical spectra. The crystal field parameters were used to analyze the crystal lattice distortions in the vicinity of the Yb³⁺ ion. Within the framework of a superposition model, it is established that four F⁻ ions located symmetrically with respect to the fourfold axis from the side of the ion-compensator approach the impurity ion and deviate from the PC axis. The second set of four fluorine ions also approaches the Yb³⁺ ion and the PC axis. The ion-compensator F⁻ also approaches considerably the impurity ion.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

On the Luminescence of Ce<Superscript>3+</Superscript>, Eu<Superscript>3+</Superscript>, and Tb<Superscript>3+</Superscript> in Novel Borate LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>

This paper reports on the photoluminescence (PL) and time-resolved properties of Ce³⁺, Eu³⁺, and Tb³⁺ in novel LiSr₄(BO₃)₃ powder phosphors. Ce³⁺ shows an emission band peaking at 420 nm under 350-nm UV excitation. Energy transfer from Ce³⁺ to Mn²⁺ takes place in the co-doped samples. Eu³⁺ shows red emission under near UV excitation. LiSr₄(BO₃)₃:Eu³⁺ phosphor could be a suitable candidate for phosphor-converted solid state lighting. The luminescence lifetime is 2.13 ms for Eu³⁺ in LiSr₄(BO₃)₃:0.001Eu³⁺. As Eu³⁺ concentration increasing, the decay curves deviate from exponential behavior. Tb³⁺ shows the strongest ⁵D₄→⁷ F₅ emission line at 540 nm. Decay curves of ⁵D₄→⁷ F₅ and ⁵D₃→⁷ F₅ emission with different Tb³⁺ concentrations were also measured. Cross-relaxation process is discussed based on the decay curves.     

Luminescence in Dy<Superscript>3+</Superscript> and Eu<Superscript>3+</Superscript> Activated K<Subscript>3</Subscript>Al<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>

The Dy³⁺ and Eu³⁺ activated K₃Al₂ (PO₄)₃ phosphors were prepared by a combustion synthesis. From a powder X-ray diffraction (XRD) analysis the formation of K₃Al₂ (PO₄)₃ was confirmed. In the photoluminescence emission spectra, the K₃Al₂(PO₄)₃:Dy³⁺ phosphor emits two distinctive colors: blue and yellow whereas K₃Al₂(PO₄)₃:Eu³⁺ emits red color. Thus the combination of colors gives BYR (blue–yellow–red) emissions can produce white light. These phosphors exhibit a strong absorption between 340 and 400 nm which suggest that present phosphor is a promising candidate for producing white light-emitting diodes (LED).     

Photodynamic processes in CaF<Subscript>2</Subscript> crystals activated by Ce<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> ions

The photochemical properties of CaF₂ crystals activated by Ce³⁺ and Yb³⁺ ions are studied. A model of the photodynamic processes induced by pumping UV or VUV radiation in active media is suggested and experimentally verified. This model explains both the presence of color centers of electronic and hole nature in crystals activated by cerium and the mechanism of suppressing of solarization processes after additional activation of the samples by Yb³⁺ ions. The cross sections of the processes of free-carrier capture by various ytterbium impurity centers are estimated. These impurity centers are established to be effective centers of recombination of free carriers of both signs.     

Luminescence of Eu<Superscript>3+</Superscript> rare-earth ions in Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

The kinetics of luminescence of Eu³⁺ ions in Lu₂O₃:Eu nanospheres with diameters of 100–270 nm and a small standard deviation of the size distribution <15% has been studied. A sharp decrease in the decay time of luminescence of Eu³⁺ ions in the red range with an increase in the diameter of nanospheres has been attributed to the appearance of a photon mode accelerating spontaneous luminescence, which is confirmed by the calculation of ranges of existence of whispering-gallery modes in studied nanospheres.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Luminescence and energy transfer mechanism in Eu<Superscript>3+</Superscript>/Tb<Superscript>3+</Superscript>-co-doped ZrO<Subscript>2</Subscript> nanocrystal rods

Nanocrystal rods of Eu³⁺/Tb³⁺-co-doped ZrO₂ were synthesized using a simple chemical precipitation technique. Both ions were successfully doped into the Zr⁴⁺ ion site in a mixed structure containing both monoclinic and tetragonal phases. The Eu³⁺ or Tb³⁺ singly doped zirconia produced red and green luminescence which are characteristics of Eu³⁺ and Tb³⁺ ions, respectively. The co-doped zirconia samples produced blue emission from defect states transitions in the host ZrO₂, red and green luminescence from dopant ions giving cool to warm white light emissions. The phosphors were efficiently excited by ultraviolet and near-ultraviolet/blue radiations giving white and red light, respectively. The decay lifetime was found to increase with increasing donor ion concentration contrary to conventional observations reported by previous researchers. Weak quadrupole–quatdrupole multipolar process was responsible for energy transfer from Tb³⁺ (donor) ion to Eu³⁺ ion. No energy back-transfer from Eu³⁺ to Tb³⁺ ion was observed from the excitation spectra. Temperature-dependent photoluminescence shows the presence of defects at low temperature, but these defects vanished at room temperature and beyond. The Eu³⁺/Tb³⁺-co-doped ZrO₂ nanocrystal rod is a potential phosphor for white light application using UV as an excitation source. Thermoluminescence measurements show that the inclusion of Tb³⁺ ion increases trap depths in the host zirconia.     

Comparative spectroscopic and laser properties of Yb<Superscript>3+</Superscript>-doped CaF<Subscript>2</Subscript>, SrF<Subscript>2</Subscript> and BaF<Subscript>2</Subscript> single crystals

We present the spectroscopic properties and room-temperature cw tunable laser operation of Yb³⁺-doped CaF₂, SrF₂ and BaF₂ single crystals grown and studied in the same conditions. Emission cross sections, lifetimes, laser thresholds, laser slope efficiencies and laser wavelength tuning ranges are compared. It appears that Yb³⁺-doped BaF₂ might be more promising for diode-pumped high power laser operation. PACS 42.55.Rz; 42.70.Hj     

CW and tunable laser operation of Yb<Superscript>3+</Superscript> doped CaF<Subscript>2</Subscript>

We present the spectroscopic properties and room temperature of a cw tunable laser operation with Yb³⁺ doped CaF₂ single crystals grown in our laboratory. A laser slope efficiency of 50% with respect to the absorbed 920 nm pump power was obtained, and the laser wavelength could be tuned between 1000 and 1060 nm. PACS 42.55R; 42.70An erratum to this article can be found at     

Ligand hyperfine interaction in Gd<Superscript>3+</Superscript> tetragonal centers in CaF<Subscript>2</Subscript> and SrF<Subscript>2</Subscript> and the structure of the impurity nearest surroundings

ENDOR experimental spectra of Gd³⁺ tetragonal impurity centers in CaF₂ and SrF₂ crystals were used to determine the superhyperfine interaction (SHFI) constants of the impurity with ¹⁹F nuclear spins of its first coordination sphere and the compensator ion. The distances in the Cd³⁺F₉ complex were estimated within the model of isotropic SHFI constants suggested in [1]. An analysis of the data on the SHFI and spin-Hamiltonian constants [2] in terms of the superposition model indicates significant changes in the contributions (due to the Gd³⁺ mixed states) to these parameters for the tetragonal centers in comparison with the corresponding contributions for the cubic and trigonal centers in the same crystals.     

Spontaneous luminescence of Eu<Superscript>3+</Superscript> ions in porous Y<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

A study of the luminescence of Eu³⁺ ions in Y₂O₃ nanospheres indicates a significant influence of the porous structure of nanoparticles on the luminescence of dopant ions. It is shown that filling the nanopores of initially porous Y₂O₃ nanospheres shortens the decay time of the spontaneous luminescence of doping europium ions. The change in the decay time is associated with the change in the effective refractive index of the porous nanospheres.     

Luminescence thermometry using Gd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript>:Eu<Superscript>3+</Superscript>

In this paper we study the possibility of using the synthesized nanopowder samples of Gd₂Zr₂O₇:Eu³⁺ for temperature measurements by analyzing the temperature effects on its photoluminescence. The nanopowder was prepared by solution combustion synthesis method. The photoluminescence spectra used for analysis of Gd₂Zr₂O₇:Eu³⁺ nano phosphor optical emission temperature dependence were acquired using continuous laser diode excitation at 405 nm. The temperature dependencies of line emission intensities of transitions from ⁵D₀ and ⁵D₁ energy levels to the ground state were analyzed. Based on this analysis we use the two lines intensity ratio method for temperature sensing. Our results show that the synthesized material can be efficiently used as thermographic phosphor up to 650 K.     

Correction of the band gap of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Submicron samples of Y₂O₃:Eu³⁺ phosphor with elevated photoluminescence (PL) efficiency and activator concentration of 9 at % obtained by the sol–gel method were investigated by diffuse reflection spectroscopy and PL spectroscopy. It is found that the diffuse reflection spectrum in the vicinity of the fundamental absorption edge (<300 nm) is distorted by the superposition of the PL of Eu³⁺ ions, as a result of which the calculated value of optical band gap E _g of the Y₂O₃ matrix is overestimated. An algorithm for eliminating the PL influence on the absorption edge is proposed, and the correct E _g values are found to be 4.61 ± 0.12 and 4.50 ± 0.12 eV for annealing at 700 and 1300°C, respectively.     

Effect of annealing temperature on the structural reorganization of Eu<Superscript>3+</Superscript> optical centers in Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>-BiOF gel films

The dependence of the structural reorganization of Eu³⁺ optical centers in Al₂O₃-Eu₂O₃-BiOF films on the annealing temperature has been investigated. It is shown by the methods of crystal field theory and computer simulation that the increase in the annealing temperature from 700 to 1100 °C leads to removal of bismuth from Eu-O-Bi complex centers with the C _3V symmetry in the Al₂O₃ structure and the change in symmetry from D ₃ to O _h for a large fraction of EuAlO₃ centers.     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.