Influence of Zn Ions Codoping on Luminescence Properties of PbWO4:RE(RE=La, Yb, Y)

Zn and RE (RE=La, Yb, Y) ions co-doped PbWO₄ (PWO) single crystal grown by the Czochralski technique are characterized by x-ray diffraction (XRD), opticaltransmission spectra, and photoluminescence (PL). The doping of Zn ions shows distinct effects on the properties of PWO:RE crystals. At low concentration of Zn ions (200ppm), the luminescence intensity is quite weak for (Zn,La)-doped PWO, but is substantially strong for (Zn,Yb)-doped PWO. The blue luminescence intensity is significantly enhanced with the increasing Zn ions doping for PWO:Y. The trivalent ions codoping can increase the ratio of the blue luminescence contributing to the fast components of light yield. Ybions can enhance efficiency of luminescence in PWO:Yb:Zn because they may act as a luminous sensitization agent which can be involved in the efficient energy transfer and storage of the radiative process.     

Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

Influence of co-doping different rare earth ions on CaGa2S4: Eu, RE(RE=Ln) phosphors

Photoluminescent phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE³⁺ including all rare earth ions except for Sc³⁺, Pm³⁺, Eu³⁺ and Lu³⁺) were prepared by sintering at high temperature in a reductive atmosphere, and their luminescent properties were studied intensively. The influences of co-doping rare earth ions on their luminescent properties were also investigated. No remarkable differences were found from excitation spectra of co-doped phosphors CaGa₂S₄: Eu²⁺, RE³⁺ in contrast with that of phosphor CaGa₂S₄: Eu²⁺, but there were a few differences in emission spectra of Ce³⁺, Pr³⁺ or Ho³⁺ co-doped phosphors. Phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE=Ce, Pr, Gd, Tb, Ho and Y) had persistent afterglow, and very short afterglow was shown for Nd³⁺ or Er³⁺ co-doped phosphors, but no long afterglow appeared when auxiliary activator was La³⁺, Sm³⁺, Dy³⁺, Tm³⁺ or Yb³⁺. Among the phosphors with long-lasting phosphorescence, in our experiments, CaGa₂S₄: Eu²⁺, Ho³⁺ had the longest and the highest brightness long yellow afterglow. Thermo-luminescence of all co-doped phosphors was measured to find the answer of different influences from different rare earth auxiliary activators.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

Radiation induced colour centers and damage in YAlO 3 :Ce and YAlO 3 :Ce,Zr scintillators

Radiation induced absorption spectra (irradiation up to 500 v Gy by 60 Co) and TSL of a set of YAP:Ce crystals co-doped by Zr 4+ were investigated. Positive effect of Zr 4+ co-doping was found, namely reduction of both the defect creation and presence of TSL active traps. Up to three absorption bands were observed in the radiation induced absorption spectra. They probably have different origin - from colour centers in the green part of the spectra to change of the Ce 3+ valency in the near UV.     

Spectral-kinetic studies of SrAlF5 doped by trivalent rare-earth ions

Photochemical properties of Ce³⁺:SrAlF₅ and Ce³⁺,Yb³⁺:SrAlF₅ single crystals together with spectroscopic and kinetic characteristics of several optically nonequivalent impurity centers and energy transfer between them are described. It is shown that co-activation by Yb³⁺ ions effectively suppresses color centers in Ce,Yb:SAF crystals. It was found out that in Ce,Yb:SAF crystals Yb ions exist simultaneously in 2+ and 3+ valent state. Three types of optically nonequivalent luminescent centers corresponding to the doublets in luminescence spectrum centered at 290, 305 and 370 nm (Ce^I, Ce^II, Ce^III, respectively) have been observed. Analysis of luminescence spectra and decays leads to the conclusion that there is no energy transfer between either cerium centers or from Ce³⁺ to Yb²⁺ apart from the Ce^III center which luminescence is slightly quenched by Yb²⁺.     

Magnetism and structural chemistry of ternary silicides: (RE,Th, U)Pt2Si2 (RE = rare earth)

Ternary silicides (RE, U, Th)Pt₂Si₂ have been prepared from the elements. All the compounds (RE= Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and U, Th) were found to be isotypic and crystallize with the primitive tetragonal CePt₂Si₂-type structure closely related to the CaBe₂Ge₂-type. The magnetic properties of these alloys were studied in the temperature range 1.5 K < T < 1100 K and in fields up to 1.3 T revealing a typical Van Vleck paramagnetism of free RE³⁺-ions for temperatures T > 200 K. A nonmagnetic ground state is reflected from the magnetic susceptibility data of CePt₂Si₂, which are interpreted in terms of interconfiguration fluctuations (ICF). The magnetic results of SmPt₂Si₂ (μ_eff = 0.7 BM) compare well with the ideal Van Vleck behavior of Sm₃₊ ions with a $\text{J =}\text{5}\text{2}$ ground state and a low-lying excited first level $\text{J =}\text{7}\text{2}$. At temperatures below 40 K antiferromagnetic ordering is found for (Gd, Tb, U)Pt₂Si₂; whereas in case of (Dy, Ho, Er, Tm)Pt₂Si₂ the onset of ferromagnetism is indicated below 4 K. None of the samples exhibited a superconducting transition above 1.8 K.     

Properties of hexagonal Al2Ge2RE (RE=Y,La,Ce,Nd,Eu,Gd,Tb,Y b and Lu) : A first-principles study

In this work, we present a study of the structural, elastic and electronic properties of the Al₂Ge₂RE (RE=Y, La, Ce, Nd, Eu, Gd, Tb, Yb and Lu) through the approaches of generalized gradient approximation (GGA) and local spin density approximation with the Hubbard energy (LSDA+U) based on density-functional theory. For most of the compounds (RE=Y, La, Ce, Nd, Eu, Yb and Lu), the results of the structural constants calculated from the approach of LSDA+U are in good agreement with the reported experimental data. Both the approaches of GGA and LSDA+U have been used to calculate DOS. Compared with the results of the GGA approach, the LSDA+U is more credible because it can show the influence of RE-f states and the RE-f states play an important role in the compound. The magnetic property has been investigated according to the result of DOS and it shows that the Al₂Ge₂Y, Al₂Ge₂La, Al₂Ge₂Y b and Al₂Ge₂Lu do not exhibit obvious magnetic property, while the other five ternary compounds are magnetic. The Voigt-Reuss-Hill (VRH) approach is used to calculate the elastic properties including bulk and shear moduli. The results of the calculated Poisson’s ratio ν and the B/G ratio demonstrate that all the Al₂Ge₂RE ternary compounds are brittle materials. The compounds, i.e. Al₂Ge₂Nd, Al₂Ge₂Eu, Al₂Ge₂Gd and Al₂Ge₂Tb which are mechanically unstable, display differences with the other five in the elastic properties.     

The luminescence of CaYBO4:RE (REEu, Gd, Tb, Ce) in VUV-visible region

Phosphors CaYBO₄:RE³⁺ (RE=Eu, Gd, Tb, Ce) were synthesized with the method of solid-state reaction at high temperature, and their vacuum ultraviolet (VUV)-visible luminescent properties in VUV-visible region were studied at 20 K. In CaYBO₄, it is confirmed that there are two types of lattice sites that can be substituted by rare-earth ions. The host excitation and emission peaks of undoped CaYBO₄ are very weak, which locate at about 175 and 350-360 nm, respectively. The existence of Gd³⁺ can efficiently enhance the utilization of host absorption energy and result in a strong emission line at 314 nm. In CaYBO₄, Eu³⁺ has typical red emission with the strongest peak at 610 nm; Tb³⁺ shows characteristic green emission, of which the maximum emission peak is located at 542 nm. The charge transfer band of CaYBO₄:Eu³⁺ was observed at 228 nm; the co-doping of Gd³⁺ and Eu³⁺ can obviously sensitize the red emission of Eu³⁺. The fluorescent spectra of CaYBO₄:Ce³⁺ is very weak due to photoionization; the co-addition of Ce³⁺-Tb³⁺ can obviously quench the luminescence of Tb³⁺.     

Evaluation of Ce3+ and alkali metal ions Co-doped LiSrAlF6 crystalline scintillators

High scintillation efficiency of Eu-doped LiSrAlF₆ (LiSAF) and LiCaAlF₆ (LiCAF) codoped with alkali metal ions has been reported in our recent studies. Thus in this paper, we demonstrated the scintillation properties of 1% Ce-doped LiSAF crystals with 1% alkali metal ions co-doping to increase the light yield and understand the scintillation mechanism. The crystals showed intense emission band corresponding to the 5d-4f transition of Ce³⁺, and their light yields under thermal neutron excitation were higher than that of the Ce only doped crystal. Especially, the light yield of Ce–Na co-doped crystal exceeded about two times that of Ce only doped one.     

NMR studies of magnetic superconductor RuSr2RECu2O8 (RE=Gd, Eu and Y)

We have carried out ^99/101Ru and ^63/65Cu nuclear magnetic resonance experiments in order to investigate magnetic and electronic properties of the magnetic superconductor RuSr₂RECu₂O₈ (RE=Gd, Eu and Y). The two kinds of ^99/101Ru signals were observed in the magnetically ordered state for each system, suggesting a charge segregation of Ru⁵⁺ (S=3/2) and Ru⁴⁺ (S=1) ions in the RuO₂ layers. The internal field at the Cu sites is revealed to be of the order of kilo Oe, indicating weak magnetic interactions between the CuO₂ and RuO₂ planes. The temperature dependence of nuclear spin-lattice relaxation time T₁ of ⁶³Cu in RE=Y shows a ‘spin gap’ like behavior, suggesting the system is under-doped.     

Luminescence of excitons and antisite defects in Lu<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

The luminescence of excitons and antisite defects (ADs) was investigated, as well as the specific features of the excitation energy transfer from excitons and ADs to the activator (Ce³⁺ ion) in phosphors based on Lu₃Al₅O₁₂:Ce (LuAG:Ce) single crystals and single-crystalline films, which are characterized by significantly different concentrations of ADs of the Lu _Al ³⁺ type and vacancy-type defects. The luminescence band with λ_max = 249 nm in LuAG:Ce single-crystal films is due to the luminescence of self-trapped excitons (STEs) at regular sites of the garnet lattice. The excited state of STEs is characterized by the presence of two radiative levels with significantly different transition probabilities, which is responsible for the presence of two excitation bands with λ_max = 160 and 167 nm and two components (fast and slow) in the decay kinetics of the STE luminescence. In LuAG:Ce single crystals, in contrast to single-crystal films, the radiative relaxation of STEs in the band with λ_max = 253.5 nm occurs predominantly near Lu _Al ³⁺ ADs. The intrinsic luminescence of LuAG:Ce single crystals at 300 K in the band with λ_max = 325 nm (τ = 540 ns), which is excited in the band with λ_max = 175 nm, is due to the radiative recombination of electrons with holes localized near Lu _Al ³⁺ ADs. In LuAG:Ce single crystals, the excitation of the luminescence of Ce³⁺ ions occurs to a large extent with the participation of ADs. As a result, slow components are present in the luminescence decay of Ce³⁺ ions in LuAG:Ce single crystals due to both the reabsorption of the UV AD luminescence in the 4f-5d absorption band of Ce³⁺ ions with λ_max = 340 nm and the intermediate localization of charge carriers at ADs and vacancy-type defects. In contrast to single crystals, in phosphors based on LuAG:Ce single-crystal films, the contribution of slow components to the luminescence of Ce³⁺ ions is significantly smaller due to a low concentration of these types of defects.     

Rare-earth ion distribution in sol–gel glasses co-doped with Al3+

Terbium spectroscopy is used to probe clustering of rare earth (RE) ions in sol–gel glasses. We use pulsed laser experiments to study energy transfer among Tb³⁺ dopants, and analyze the fluorescence decay curves using the Inokuti–Hirayama model. The analysis yields new insights about the role of Al³⁺ co-doping. Assuming a multipolar interaction, we derive an effective Tb³⁺ concentration for a series of samples with varying amounts of RE. When actual doping concentration is varied over 2 orders of magnitude, the effective Tb³⁺ concentration of centers that emit light changes by only a factor of 10. The results indicate that Al³⁺ co-doping is only effective at dispersing RE ions when the ratio of Al:RE is 10:1 or greater. At higher RE concentrations, most ions reside in clusters; ⁵D₃ fluorescence is observed from a minority of isolated ions. This interpretation contradicts earlier work that used fluorescence line narrowing to demonstrate that Al³⁺ co-doping caused RE dispersal at high doping levels.     

Gamma-ray induced color centers in Yb:YAG crystals grown by Czochralski method

20 at.% Yb:YAG single crystals have been grown by the CZ method and gamma-ray irradiation induced color centers and valence change of Fe³⁺ and Y b³⁺ ions in Yb:YAG have been studied. One significant 255 nm absorption band was observed in as-grown crystals and was attributed to Fe³⁺ ions. Two additional absorption (AA) bands located at 255 nm and 345 nm, respectively, were produced after gamma irradiation. The changes in the AA spectra after gamma irradiation and air annealing are mainly related to the charge exchange of the Fe³⁺, Fe²⁺, oxygen vacancies and F-type color centers. Analysis shows that the broad AA band is associated with Fe²⁺ ions and F-type color centers. The transition Y b³⁺→Y b²⁺ takes place as an effect of recharging of one of the Y b³⁺ ions from a pair in the process of gamma irradiation.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

Enhanced luminescence and degradation of SiO2:Ce,Tb powder phosphors prepared by a sol-gel process

Enhanced green photoluminescence and cathodoluminescence (CL) from Tb³⁺ ions due to co-doping with Ce³⁺ ions were observed from SiO₂:Ce,Tb powder phosphors prepared by a sol-gel technique. Blue emission from the Ce³⁺ ions was completely suppressed by Tb co-doping, presumably due to energy transfer from Ce³⁺ to Tb³⁺. In addition, the green CL intensity from SiO₂:Ce,Tb degraded by ∼50% when the powders were irradiated for 10 h with a 2 keV, 54 mA/cm² beam of electrons in an ultra-high vacuum chamber containing either 1×10⁻⁸ or 1×10⁻⁷ Torr O₂. Desorption of oxygen from the surface was observed during the decrease of CL intensity. The mechanisms for energy transfer from Ce³⁺ ions to Tb³⁺ ions to enhance the green luminescence, and mechanisms for desorption of oxygen from the phosphor surface that would result in decreased CL intensity are discussed.     

Photoluminescence spectra of rare earth doped CaGa2S4 single crystals

Six kind CaGa₂S₄ single crystals doped with different rare earth (RE) elements are grown by the horizontal Bridgman method, and their photoluminescence (PL) spectra are measured in the temperature range from 10 to 300 K. The PL spectra of Ce or Eu doped crystals have broad line shapes due to the phonon assisted 4f-5d transitions. On the other hand, those of Pr³⁺, Tb³⁺, Er³⁺ or Tm³⁺ doped samples show narrow ones owing to the 4f-4f transitions. The assignments of the electronic levels are made in reference to the reported data of RE 4f multiplets observed in same materials.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Anisotropic magnetic susceptibility of erbium and ytterbium in zircon,ZrSiO4

Magnetic susceptibility measurements have been made for both Er- and Yb-doped (1&#x0303;0³ppm) zircon single crystals with the magnetic field perpendicular and parallel to the [001] axis. Large susceptibility anisotropies were found in both cases. Our observed anisotropies of ZrSiO₄: Yb indicate small populations (1&#x0303;9%) of Yb ions at the axial (tetragonal) sites, as the susceptibility of ZrSiO₄: Yb would be nearly isotropic if the Yb ions only occupied the orthorhombic sites. For Er³⁺ in orthorhombic sites of zircon, our data indicate that the first excited state is paramagnetic with g_x = 9 and g_y 5&#x0303; at 20 cm^?1 above the ground state (g_x 0&#x0303;, g_y 1&#x0303;5). The first excited state is quite similar to the ground states observed for Er³⁺ in many host lattices