Growth and the luminescence properties of a lutetium gadolinium garnet doped with Ce3+ and Pr3+ ions

Crystals of lutetium gadolinium garnet solid solutions (Lu_{1 − x} Gd _x )Al₅O₁₂ (0 ≤ x ≤ 0.6) doped with Ce³⁺ and Pr³⁺ ions have been prepared by the horizontal directional crystallization method, and their optical and luminescence properties have been investigated. It has been established that the introduction of gadolinium into the lutetium garnet lattice leads to a decrease in the antisite luminescence (Lu_Al centers) in the UV spectral range and to sensitization of the Ce³⁺ ion luminescence. By contrast, the presence of gadolinium results in the quenching of the Pr³⁺ luminescence due to the nonradiative excitation transfer from Pr³⁺ ions to Gd³⁺ ions.     

Doped ions (Co2+, Fe3+) tuning morphologies and magnetic properties of indium oxide nanoparticles

Transition-metal ion-doped indium oxide was potentially used in spintronic devices. In this article, 10 at.% Co²⁺- and Fe³⁺-doped indium oxide nanocrystals were, respectively, prepared by direct solvothermal method. The influences of doped ions on their morphologies and magnetic properties of indium oxide nanocrystals were investigated. It was found that the doped ions could tune the microscopic morphologies and crystalline structures of indium oxide nanoparticles. Co²⁺-doped samples were polycrystalline nanoflowers aggregated by about 5 nm nanocrystals while Fe³⁺-doped specimens were single-crystalline nanocubes with crystalline sizes of about 16 nm. Meanwhile, the magnetic transition from diamagnetism to paramagnetism was also realized by doping Co²⁺ or Fe³⁺ ions into the indium oxide host matrices. In addition, their magnetic properties were further demonstrated to be intrinsic and not caused by impurities.     

铈掺杂氧化铝薄膜的蓝紫色发光特性

应用中频反应磁控溅射技术制备了Al₂O₃:Ce³⁺的非晶薄膜.X射线光电子谱(XPS)检测显示薄膜中有Ce³⁺生成.这些薄膜的光致发光峰是在374nm附近,它来自于Ce³⁺离子的5d¹激发态向基态4f¹的两个劈裂能级的跃迁.发光强度强烈地依赖于薄膜的掺杂浓度,但发光峰位置不随掺杂浓度而变化.Ce³⁺含量和薄膜的化学成分是通过X射线散 关键词： 光致发光 2O₃')" href="#">Al₂O₃ 薄膜 稀土元素     

New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions

The moving single-bubble sonoluminescence of Ce³⁺ in water and ethylene glycol solutions of CeCl₃ and (NH₄)₂Ce(NO₃)₆ was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10^–4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce⁴⁺ reduction by a solvated (or hydrated in water) electron: Ce⁴⁺ + e_s (e_aq) → *Ce³⁺. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl₃ solutions, the Ce⁴⁺ ion is formed at the oxidation of Ce³⁺ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br⁻ (acceptor of OH) and H⁺ ions (acceptor of e_aq). In water and ethylene glycol solutions of (NH₄)₂Ce(NO₃)₆, the sonochemiluminescence also quenched by the H⁺ ion. The sonochemiluminescence in CeCl₃ solutions is registered at [Ce³⁺] ≥ 10^–5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10^–2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce³⁺ in solutions with [Ce³⁺] ≥ 10^–4 M. If the cerium concentration is more than 10^–2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce³⁺ ions penetrating into the moving bubble.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.     

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.     

The luminescence and energy transfer in Pr3+–Ce3+ co-doped Lu0.8Sc0.2BO3 crystals

Lu_0.8Sc_0.2BO₃ crystals doped with 1 at%Ce³⁺ and co-doped 0.1 at% and 0.5 at%Pr³⁺ were grown by the Czochralski method. The concentrations of Pr³⁺ and Ce³⁺ in crystals were measured by the ICP-AES method. Absorption spectra, VUV–UV spectra, fluorescence decay time and X-ray excitation luminescence spectra were investigated at room temperature. The excitation luminescence spectra of Ce³⁺ emission and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configurations of the Pr³⁺ and Ce³⁺ conspicuously indicated the non-radiative energy transfer from Pr³⁺ to Ce³⁺. The detailed pathways were shown in the energy level diagram of the respective Ce³⁺ and Pr³⁺ in Lu_0.8Sc_0.2BO₃ host. In addition, the scintillation efficiency data indicated that the energy transfer effect is directly associated with the Pr³⁺ concentration.     

Luminescence study of the LuBO3 and LuPO4 doped with RE3+

Lutetium borates and phosphates doped with RE³⁺ ions are perspective scintillators. In the paper, the results of the luminescence spectroscopy of LuPO₄ and LuBO₃ doped with Pr³⁺, Ce³⁺, Tb³⁺ and Eu³⁺ under synchrotron radiation excitation are presented. The processes of the energy transfer from the host lattice to the luminescence centers are considered. The creation of excitons at the edge of fundamental absorption region is shown. The bandgap values for lutetium borate and phosphate were estimated.     

Enhanced hydrogen production by doping Pr into Ce0.9Hf0.1O2 for thermochemical two-step water-splitting cycle

We synthesized (Ce_0.9Hf_0.1)_1−xPr_xO_2−δ (x=0, 0.05 and 0.1) using the polymerized complex method. The synthesized samples, as well as the samples after thermochemical two-step water-splitting cycles have a fluorite structure and Pr exists in the solid solutions with both trivalent and tetravalent states, as suggested by powder X-ray Diffraction (XRD) Patterns. The reduction fraction of Ce⁴⁺ in redox cycles (oxidation step in air) and two-step water-splitting cycles (oxidation step in steam) indicates that the addition of Pr into Ce–Hf oxide solid solution cannot improve the reduction fraction of Ce⁴⁺ during the redox cycles but both the reduction fraction of Ce⁴⁺ and H₂ yield are significantly enhanced during two-step water-splitting cycles. The chemical composition of 10 mol% Pr doped Ce_0.9Hf_0.1O₂ exhibits the highest reactivity for hydrogen production in H₂-generation step by yielding an average amount of 5.72 ml g⁻¹ hydrogen gas, which is much higher than that evolved by Ce_0.9Hf_0.1O₂ (4.50 ml g⁻¹). The enhancement effect of doping Pr on the performance during two-step water-splitting cycles is because of the multivalent properties of Pr, which can: (1) reduce the amount of Ce³⁺ oxidized by contamination air (contamination air eliminated by partial oxidation of Pr³⁺ to Pr⁴⁺) in H₂-generation step; (2) enhance the reaction rate in H₂-generation step by improving the ionic conductivity (extrinsic oxygen vacancies created by the substitution of Ce⁴⁺ by Pr³⁺).     

Evolution of microstructure and dielectric properties of (LiCe)-doped Na0.5Bi2.5Nb2O9 Aurivillius type ceramics

Aurivillius type (NaBi)_0.5?x(LiCe)_xBi₂Nb₂O₉ ceramics were prepared by the standard ceramics route. The single crystal structural ceramics were achieved for all compositions and lattice distortion was decreased by (LiCe) dopants. The temperature dependent dielectric properties revealed that all compositions possess a high Curie-temperature (>780 °C). A modified Curie–Weiss relationship is used to study the diffuseness behavior of a ferroelectric phase transition indicating the degree of diffuseness of NBN-based ceramics increased with (LiCe) modifications. The degradation of resistance implied a plausible model that Ce⁴⁺ ions entered into the B-site of the pseudo-perovskite structure and acted as acceptor doping. Further investigation demonstrated that both electrical conduction and dielectric relaxation processes were associated with the oxygen vacancies produced by the substitution of Nb⁵⁺ ions by the Ce⁴⁺ ions.     

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.     

Electronic excitations and luminescence of SrAlF5 crystals doped with Ce3+ ions

This paper reports the results of a time-resolved photoluminescence and energy transfer processes study in Ce³⁺ doped SrAlF₅ single crystals. Several Ce³⁺ centers emitting near 4 eV due to 5d-4f transitions of Ce³⁺ ions substituting for Sr²⁺ in non-equivalent lattice sites were identified. The lifetime of these transitions is in the range of 25–35 ns under intra-center excitation in the energy region of 4–7 eV at T = 10 K. An effective energy transfer from lattice defects to dopant ions was revealed in the – 7–11 eV energy range. Both direct and indirect excitation channels are efficient at room temperature. Excitons bound to dopants are revealed at T = 10 K under excitation in the fundamental absorption region above 11 eV, as well as radiative decay of self-trapped excitons resulting in luminescence near 3 eV.     

Stepwise synthesis of fine crystalline Ce-doped yttrium aluminum garnet in water medium in subcritical and supercritical conditions

In this paper the continuous stepwise method of a production of fine crystalline yttrium aluminum garnet doped with cerium (YAG: Ce³⁺) in supercritical water fluid (SCWF) are represented. The synthesis was carried out in water medium in two stages: first in subcritical conditions and then in an atmosphere of supercritical water fluid. The stoichiometric mixture of yttrium oxide and aluminum hydroxide in a water solution of cerium nitrate was maintained the certain time at 280°C and under vapor water pressure 6.3 MPa. Then temperature and pressure were risen up to a supercritical condition (T = 392–400°C, P_{H2 O}P_{H_2 O} = 22 MPa). The concentration of cerium ions in reaction medium was changed in the interval 0.012–0.706 wt %. The products, obtained on various stages of synthesis, were investigated by physical-chemical methods. During the first stage, the crystals of boehmite and yttrium hydroxide under hydrothermal conditions were arising, and eventually poorly formed YAG: Ce³⁺ were appearing. At this stage, the diffusion of cerium ions into intermediate products takes place. Because of this, at the second step of synthesis, in supercritical conditions, YAG: Ce³⁺, phosphor with high luminescence intensity at 530 nm, was obtained. In supercritical conditions well-faceted crystals of 0.5–3.0 μm with rhombododecahedral habitus were produced.     

Effect of cerium oxide on the precipitation of silver nanoparticles in femtosecond laser irradiated silicate glass

We investigated the effect of cerium oxide on the precipitation of Ag nanoparticles in silicate glass via a femtosecond laser irradiation and successive annealing. Absorption spectra show that Ce³⁺ ions may absorb part of the laser energy via multiphoton absorption and release free electrons, resulting in an increase of the concentration of Ag atoms and a decrease of the concentration of hole-trapped color centers, which influence precipitation of the Ag nanoparticles. In addition, we found that the formed Ag⁰ may reduce Ce⁴⁺ ions to Ce³⁺ ions during the annealing process, which inhibits the growth of the Ag nanoparticles. PACS 78.55.Qr; 78.67.Bf; 81.05.Pj     

Effect of La3+ and Pr3+ co-doping on structural,thermal and electrical properties of ceria ceramics as solid electrolytes for IT-SOFC applications

In the present investigation, the effect of La³⁺ and Pr³⁺ co-doping on structural, thermal and electrical properties of ceria ceramics useful as solid electrolytes in intermediate temperature solid oxide fuel cells (IT-SOFCs) has been studied. The co-doped ceria Ce_0.8Pr_0.2–xLa_xO_2-δ samples have been prepared successfully via sol-gel auto-combustion synthesis. The high dense ceramic samples have been achieved by carry out an optimized conventional sintering at 1300 °C for 4 h. The powder X-ray diffraction analysis of all the co-doped ceria ceramics revealed the single phase with cubic-fluorite structure formation. Crystallographic information has been carried out from the powder X-ray diffraction and Rietveld refinement analysis. The scanning electron microscope and energy dispersive spectroscopy analysis revealed the smaller grain size with high density in microstructure and stoichiometric elemental confirmations. Raman spectra of prepared ceramics revealed the information of phase and oxygen vacancy formation in the entire compositions. The dilatometric studies of prepared co-doped ceria ceramics revealed the moderate coefficients of thermal expansion. The electrical parameters such as total conductivities and activation energies have been studied with the help of impedance spectroscopy. Among all these co-doped ceria ceramic samples, Ce_0.80Pr_0.10La_0.10O_2−δ found to exhibit the highest value of total ionic conductivity with minimum activation energy and this makes it could be a promising electrolyte material for IT-SOFC applications.     

Ceria co-doped with calcium (Ca) and strontium (Sr): a potential candidate as a solid electrolyte for intermediate temperature solid oxide fuel cells

Co-doped samples of Ce_0.95?x Ca_0.05Sr _x O_1.95?x , where (x?=?0.00, 0.01, 0.02, and 0.03), have been prepared by auto-combustion method and characterized to explore their use as a solid electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). Crystal structure, microstructure, and ionic conductivity have been characterized by X-ray diffraction, scanning electron microscopy, and impedance spectroscopy, respectively. All the compositions have been found to be single phase. Results show that the samples co-doped with Ca and Sr exhibit higher ionic conductivity than the samples singly doped with Ca in the intermediate temperature range. Ce_0.93Ca_0.05Sr_0.02O_2?δ exhibits maximum conductivity among all the compositions. This may be a potential candidate as a solid electrolyte for IT-SOFCs.     

Time-resolved luminescence spectroscopy of pure and doped with Ce3+ ions SrAlF5 crystals

The results of a study of time-resolved photoluminescence (PL) and energy transfer in both pure and doped with Ce³⁺ ions SrAlF₅ (SAF) single crystals are presented. The time-resolved and steady-state PL spectra in the energy range of 1.5–6.0 eV, the PL excitation spectra and the reflectivity in the energy range of 3.7–21 eV, as well as the PL decay kinetics were measured at 8.8 and 295 K. The lattice defects were revealed in the low temperature PL spectra (emission bands at 2.9 and 4.5 eV) in the undoped SAF crystals. The luminescence spectra of the doped Ce³⁺:SAF crystals demonstrate a new selective emission bands in the range of 3.7–4.5 eV with the exponential decay kinetics (τ ≈ 60 ns at X-ray excitation). These bands correspond to the d-f transitions in Ce³⁺ ions, which occupy nonequivalent sites in the crystal lattice.     

Effect of the valence state of ce ions on the phase stability and mechanical properties of the crystals of ZrO<Subscript>2</Subscript>-based solid solutions

The structure and mechanical properties of the crystals of solid solutions of zirconium dioxide, which are stabilized by yttrium and cerium oxides, have been studied. The electron paramagnetic resonance technique has been used to identify Ce³⁺ ions and to determine their relative concentration in the crystals. It is shown that the presence of Ce³⁺ ions in the crystals is the main factor responsible for their high fracture toughness. The annealings carried out during investigations, which lead to a decrease in the concentration of Ce³⁺ ions, show that a change in the valence state of cerium ions lowers the fracture toughness of the crystals.     

Spectroscopic properties of a Ce3+Tm3+ center in CsCdBr3 crystals: Absorption,emission, and energy transfer

When crystals of CsCdBr₃ are doped with trivalent cerium and thulium, it appears that Ce³⁺-vacancy-Tm³⁺ centers are formed. A very efficient cerium to thulium energy transfer is observed in this center when the doped crystals are irradiated at the energy (～ 27800 cm^?1) corresponding to the 4f → 5d transition of Ce³⁺. Spectroscopic studies indicate that the energy transfer begins to diminish when the temperature is raised above 100 K. At room temperature the doped crystals show no detectable energy transfer.     

Emergence of Paramagnetism in Organic Macromolecules during Synthesis

Paramagnetism in polyaniline can be generated during synthesis if cerium (IV) ammonium nitrate (CAN) is used as a polymerizing (oxidizing) agent. During the reaction, in situ formation of Ce³⁺ ions are doped in the spherical polyaniline particles and show paramagnetic behavior throughout the experimental temperature range (400–1.9 K). The result indicated that the Ce³⁺ ions covalently functionalized with the chain nitrogen of the polyaniline.