Conversion of the valence states of Eu ions in YVO4 with the gamma-ray irradiation

We investigated the effect of the gamma-ray irradiation on the emission property of the Eu ion doped YVO₄. We clearly observed that on exposure to the gamma-ray, sharp emission peaks originating from the Eu³⁺ ions were suppressed dramatically. Instead, a broad emission feature near 470 nm, which was attributed to the Eu²⁺ ions, emerged. The quantitative analysis on the emission spectra suggest that the valence state of the Eu ions in our samples was changed from 3 + to 2 + by the gamma-ray irradiation. The conversion of the valence state of the Eu ions was closely related to the formation of the oxygen vacancies induced by the gamma-ray irradiation.     

Photoelectron spectra and surface valence fluctuation of Eu in the misfit-layer compound {(EuS)1.15}1.5NbS2

The 1.5Q/1 H type of the misfit layer compound {(EuS)_1.15}_1.5NbS₂ has been studied by X-ray photoelectron spectroscopy. Eu 3d, 4d, 4f and 5p spectra are measured with Al and MgKα radiation. Their intensities are analyzed, taking the escape depth of photoelectrons emitted from the core levels into account. The results indicate that valence transfer of nearly-half Eu²⁺ ions to Eu³⁺ happens in the outermost surface layer and a reduced Eu–S distance brings about surface rearrangement. It is confirmed that Eu²⁺ and Eu³⁺ coexist in a bulk, in consistency with bond valence calculations and Mössbauer spectra. The XPS spectra are well interpreted in terms of the multiplet structures of Eu²⁺ and Eu³⁺.     

Influence of co‐dopant in the europium reduction in SrAl2O4 host

Xerogels of strontium chlorate and aluminium chlorate doped with europium (un‐co‐doped) and co‐doped with rare earth ions (Ln = Gd, Dy, Er and Y) were prepared using the proteic sol–gel route. Synchrotron radiation was used to investigate the effect of different co‐dopants on the Eu³⁺→ Eu²⁺ reduction process during the synthesis of the samples. Samples were excited at the Eu L_III‐edge and the XANES regions were analyzed. The results suggest that some of the Eu ions can be stabilized in the divalent state and that it is difficult to completely reduce Eu³⁺ to Eu²⁺ during thermal treatment. The mechanisms of the Eu reduction processes are explained by a proposed model based on the incorporation of charge‐compensation defects.     

A Mössbauer study of La1−xEuxB6 compounds synthesized at high pressure and temperature

A series of hexaborides La_1?xEu_xB₆ (x=0.0–1.0) were synthesized under a pressure of 3.5 GPa and at a temperature of 1600^○C using La₂O₃, Eu₂O₃ and amorphous boron as the starting materials. The products were characterized by X‐ray Diffraction (XRD) and Mössbauer spectroscopy. XRD data analysis shows that all samples crystallize in a cubic CsCl‐type structure, and the cell volume increases with x. Room temperature ¹⁵¹Eu Mössbauer measurements reveal that Eu ions in all samples are in the divalent state, except for the x=1.0 sample where a small amount of Eu³⁺ ions was detected. The quadrupole splitting of the Eu²⁺ ions is positive. Eu ions were reduced from trivalent to divalent during the high‐pressure and ‐temperature processes. The isomer shifts of the Eu²⁺ ions are all smaller than ?12.5 mm/s, suggesting that there is no valence fluctuation in the samples. The hexaborides doped by divalent Eu are not metallic.     

Probing of surface Eu ions present in ZnO:Eu nanoparticles by covering ZnO:Eu core with Y2O3 shell: Luminescence study

Eu³⁺ doped ZnO nanoparticles are known to have significance extent of surface Eu³⁺ ions due to a large difference in ionic radii. Effect of such Eu³⁺ ions on the luminescence properties of ZnO:Eu nanoparticles has been understood from the luminescence studies of ZnO:Eu nanoparticles covered with Y₂O₃ shell. Based on the asymmetric ratio of luminescence and extent of energy transfer, it is established that when ZnO:Eu nanoparticles are covered with Y₂O₃ shell, a part of Eu³⁺ ions present with ZnO:Eu core migrate to Y₂O₃ shell and occupy Y³⁺ lattice positions.     

Photoluminescence and radioluminescence study of Eu and Mn doped RbMgF3 nanoparticles

Photoluminescence (PL) and radioluminescence (RL) measurements were made on RbMgF₃ nanoparticles doped with Mn or Eu. We find that the Mn doped samples contain only Mn²⁺ and the Eu doped samples contained Eu³⁺ and Eu²⁺. The Mn²⁺ PL lifetimes are nearly independent of Mn²⁺ concentration but the RL spectra increases at high doses for 1% Mn²⁺ and decreases slightly at high doses for 5% Mn²⁺. The 5% Mn²⁺ is more radiation hard and the integrated RL intensity only starts to significantly decrease above 1 kGy. The Eu doped sample displays a PL lifetime that is lower for high Eu concentrations and this can be accounted for by a model where there is energy transfer between Eu³⁺ and more nonradiative decay sites at the surface. The RL is independent of dose between 10 mGy and ∼200 Gy, where the 1% Eu sample is more radiation hard and the Eu³⁺ RL intensity has decreased by only 3.4% at 6.7 kGy.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

Luminescence in BaSO4:Eu

Abstract

Photoluminescence and thermoluminescence in BaSO₄:Eu is reported. In earlier works, divalent Eu has been studied in BaSO₄. In the present work Eu was incorporated as in predominantly Eu³⁺ or Eu²⁺ form. It is shown that RE³⁺ ? RE²⁺ conversion or RE²⁺ ? RE⁺ conversion is not an integral part of gamma induced TL. Eu³⁺ ? Eu²⁺ conversion, on the other hand, may be important in UV induced TL. Low UV efficiency of this material is attributed to poor Eu³⁺ ? Eu²⁺ conversion. This is in quite contrast to the analogus material CaSO₄: Eu.     

Valence averaging and phase transitions in europium (Eu2VO4) and iron (RSr2Fe3O9) compounds

Mössbauer studies of ¹⁵¹Eu in Eu₂VO₄ reveal a very sharp valence averaging phase transition at 450 K. Two equally intense absorption lines, differing in isomer shift by 12.7 mm/s, corresponding to Eu²⁺ and Eu³⁺, collapse to a single absorption line at the average isomer shift. The transition is confirmed by X-ray and resistivity measurements. In RSr₂Fe₃O₉ (R=Pr, Sm) ⁵⁷Fe studies reveal averaging valence phase transitions coinciding with magnetic order phase transitions at 190 K and 140 K, respectively. Two magnetic sextets, corresponding to 2Fe³⁺ + Fe⁵⁺, collapse to two singlets corresponding to 2Fe⁴⁺ + Fe³⁺.     

Influence of phase and morphology on thermal conductivity of alumina particle/silicone rubber composites

Eu²⁺- and Eu³⁺-Zn₂GeO₄ were prepared by the high temperature solid-state reaction method. The phase purity and crystallinity of Zn₂GeO₄:Eu samples were characterized by X-ray diffraction (XRD). The excitation spectra, the emission spectra and the luminescence decay curves of the Eu²⁺- and Eu³⁺-Zn₂GeO₄ were investigated. Zn₂GeO₄:Eu²⁺ gives a bluish-green luminescence with one emission band located at 467 nm, and Zn₂GeO₄:Eu³⁺ presents an reddish-orange color due to the transition (⁵D₀→⁷F_J, J = 1 and 2) of the Eu³⁺ ions. The luminescence decay curves of Eu²⁺ and Eu³⁺ provide complementary evidence to the mixed valence of europium (Eu²⁺, Eu³⁺) in Zn₂GeO₄ host. These indicate that the mixed valence of europium (Eu²⁺, Eu³⁺) coexists in Zn₂GeO₄ host prepared in an oxidizing atmosphere. The abnormal reduction phenomenon of Eu³⁺→Eu²⁺ in Zn₂GeO₄ host prepared in an oxidizing atmosphere was reported and discussed on the basis of the charge compensation model.     

Self-compensation characteristics of Eu ions in BaTiO3

In order to clarify whether the mixed valence of Eu²⁺/Eu³⁺ exists in a self-compensation mode in Eu-doped BaTiO₃, the site occupation and valence state of Eu ions in barium titanate were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), Raman spectroscopy (RS), and dielectric measurements. The results indicate that Eu ions may enter both Ba- and Ti-sites as Eu³⁺, forming a self-compensation mode with the amphoteric behavior. Self-compensation characteristics of Eu ions in BaTiO₃ are reflected by an expansion in unit cell volume, evolution of the 830 cm^− 1 Raman band, strong diffusion of the dielectric peak, disappearance of the Eu²⁺ ESR broad signal, and a g = 2.004 signal independent of temperature.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

Mössbauer effect study of Gd- and Eu-doped CaSO4

Mössbauer spectra have been taken of rare earth doped CaSO₄ using the¹⁵¹Eu and¹⁵⁵Gd transitions. Site assignments have been made to the five principal Gd³⁺ configurations principally on the basis of point charge calculations. We were unable to distingiush different Eu³⁺ sites and no conversion of Eu³⁺ to Eu²⁺ could be observed after prolonged x-irradiation.     

Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

Luminescence and scintillation of Eu2+‐doped high silica glass

High silica glass doped with Eu²⁺ ions was prepared as a scintillating material by impregnation of Eu ions into a porous silica glass followed by reduction sintering in CO atmosphere. A dominant emission band of the Eu²⁺ 5d–4f transition peaking around 430 nm was observed in the luminescence spectrum with the excitation peak around 280 nm and no emission from Eu³⁺ was present. Photoluminescence decay kinetics was governed by decay times of a few microseconds. The Eu²⁺‐doped high silica glass exhibited comparable energy resolution and slightly higher photoelectron yield with respect to the Bi₄Ge₃O₁₂ crystal in the pulse height spectra for X‐ray photon energies within 22–60 keV. Furthermore, a factor of 1.2 higher radioluminescence intensity was observed as well. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

共溅射和离子注入制备的SiO2(Eu)薄膜中Eu3+到Eu2+的转变

采用共溅射方法和Eu离子注入热生长的SiO₂方法得到SiO₂(Eu)薄膜,Eu离子的浓度为4%和0.5%.对样品X射线吸收近边结构(XANES)的研究和分析表明,在高温氮气中发生了Eu³⁺向Eu²⁺的转变.SiO₂(Eu)薄膜高温氮气退火下蓝光的发射证明了这一结论 关键词： 2(Eu)薄膜')" href="#">SiO₂(Eu)薄膜 XANES     

Pressure dependence of interconfiguration fluctuations in Eu0.25La0.75Rh2.00 studied by Mossbauer spectroscopy

The effect of pressure on the 21.6 keV Mössbauer resonance of ¹⁵¹Eu in Eu_0.25La_0.75Rh_2.00 was studied at various temperatures. The strong pressure induced shift of the resonance lines can be described by an increase of the energy separation between the Eu²⁺ and Eu³⁺ valence states.     

Photoluminescence of Eu single doped and Eu/Dy codoped Sr2Al2SiO7 phosphors with long persistence

This paper reports the preparation of long persistent Sr₂Al₂SiO₇:Eu²⁺ and Sr₂Al₂SiO₇:Eu²⁺, Dy³⁺ phosphors and the comparison of their photoluminescent properties. The silicate phosphors prepared by solid-state reaction routine showed a broad blue emission peaking at 484 nm when activated by UV illumination. Such a bluish-green emission can be attributed to the intrinsic 4f-5d transitions of Eu²⁺. After the UV source was switched off, long persistent phosphorescence could be observed by naked eyes for both samples in darkness. Afterglow measurements revealed that Eu/Dy codoped phosphor possesses better afterglow properties than the Eu single doped one, since the maximum lifetime (τ_max=99 s) of the photons calculated from the decay profile is much larger than that of the Eu single doped phosphor (τ_max=82 s). TSL results suggested that the difference in afterglow properties was caused by the difference in the electron traps within the crystal lattice. For Eu/Dy codoped phosphor, the doping of Dy ions produced electron traps with trap depth of 0.52 eV, which is suitable and therefore leads to good persistence. However, in the case of Eu single doped phosphor, the trap depth is 0.88 eV, which is really too deep an energy barrier to overcome, and therefore a poor persistence was observed in the experiment.     

Eu2+ and Eu3+ based “concentrated phosphors” as converters for UV LED light: two approaches and two new examples

The absolute majority of phosphors are composed of a host lattice and some percentage of an activator. At higher activator concentrations the concentration quenching occurs. However, there are phosphors in which only minor quenching of the emission occurs with increasing of the activator content. Based on the existence of two different valence states of the Eu ion (2+ and 3+), two approaches for the development of “concentrated phosphors”, i.e. light emitting materials in which the activator ion is a main part of the crystal lattice, are discussed. In both approaches, reduced energy migration leading to the luminescence quenching is considered as a main condition to reach a high quantum efficiency of a concentrated phosphor. Two kinds of phosphors—Eu²⁺-doped alumosilicate and Eu³⁺-doped oxyfluoride—are used as an experimental basis for this discussion. Starting from the stoichiometric Ca_1-xEu_x²⁺Al₂Si₂O₈\mathrm{Ca}_{1-x}\mathrm{Eu}_{x}^{2+}\mathrm{Al}_{2}\mathrm{Si}_{2}\mathrm{O}_{8} anorthite and Eu³⁺OF oxyfluorides, the non-stoichiometric powders with Eu²⁺_0.92Al_1.76Si_2.24O₈\mathrm{Eu}^{2+}_{0.92}\mathrm{Al}_{1.76}\mathrm{Si}_{2.24}\mathrm{O}_{8}, Eu³⁺(O, F)_2,35 and Eu³⁺(O, F)_2,16 compositions were synthesized by a solid state reaction and investigated. It was shown that—in spite of the almost 100% Eu concentration—light converters with high quantum efficiency of more than 45% can be realized. A possible application of these materials as UV LED light converters for white light emitting diodes are discussed as well.     

Eu(TTFA)3掺杂SiO2杂化胶体球的合成及特性

采用改进的碱催化法和种子法分别制得了稀土配合物Eu(TTFA)₃掺杂的SiO₂杂化胶体球,并用透射电子显微镜和荧光分光光度计对其显微形貌和荧光光谱特性进行了详细地研究.结果表明,两种方法都可以获得单分散性的、稀土配合物掺杂SiO₂杂化胶体球,且都具有Eu³⁺离子典型的荧光光谱特性.Eu(TTFA)₃掺杂入SiO₂胶体球中后,有机配体TTFA在短波长处的吸收明显增强了,最大的吸收峰位也向短波长方向移动大约20～30 nm,Eu³⁺离子5D0→7F2发射跃迁仍然具有良好的窄线发光特征,同时荧光峰值的形态和位置受SiO₂基体的影响发生轻微的变化.