EPR of Ce<Superscript>3+</Superscript> ions in mixed yttrium-lutecium orthoaluminates

The results of EPR studies of Ce³⁺ ions incorporated into single crystals of mixed yttrium-lutecium orthoaluminates Y_1?xLu_xAlO₃ (YLuAP, x=0.1, 0.3) are reported. In compositionally disordered YLuAP compounds, in comparison to YAlO₃, new paramagnetic Ce³⁺ centers are found. These centers are caused by the changes in symmetry and in the crystal field magnitude due to the isomorphic substitution of Y³⁺ ions by Lu³⁺ in the yttrium sublattice of orthoaluminates. It is shown that the formation of 27 different types of centers is possible in YLuAP with variation of the Lu content. The probabilities of formation of new paramagnetic centers are calculated.     

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.     

Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Intensities of hypersensitive transitions in garnet crystals doped with Er<Superscript>3+</Superscript> ions

We examine the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of yttrium-aluminum, scandium-containing, and gallium garnet crystals doped with Er³⁺ ions. A comparative analysis of the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of garnets with different contents of Al³⁺ and Sc³⁺ ions (Gd_2.4Er_0.5Sc_1.8Al_3.3O₁₂, Gd_2.4Er_0.5Sc_1.9Al_3.2O₁₂, Gd_2.4Er_0.5Sc_2.0Al_3.1O₁₂) is performed, as a result of which the oscillator strengths and the intensity parameters Ω _t (t = 2, 4, 6) of these crystals are shown to have close values. We find that Ca₃(NbGa)₅O₁₂ crystals doped with Er³⁺ ions are characterized by highest values of the oscillator strengths for hypersensitive transitions and of the intensity parameter Ω₂ of Er³⁺ ions compared to the values of these quantities in the examined garnet crystals, which is determined by the fact that the symmetry of the local environment of Er³⁺ ions in these crystals is C ₁, C ₂, or C _2ν. We reveal that, as the concentration of Er³⁺ ions in these crystals increases from 1 to 39 at %, both the oscillator strength of the hypersensitive transition ⁴ I _15/2 → ² H _11/2 of Er³⁺ ions and their intensity parameter Ω₂ tend to decrease, which can be related to an increase in the relative fraction of Er³⁺ ions with higher symmetry of the local environment.     

Spectroscopic and laser properties of Er3+-doped monoclinic BaY2F8 single crystals

The luminescence and absorption properties of Ba(Y_1−x Er _x )₂F₈ (x=0.001, 0.01, 0.05, 0.1, 0.2 and 0.3) and the Er³⁺-ion decay kinetics of luminescent transitions from three initial laser states, the⁴S_3/2,⁴F._9/2 and⁴I_11/2 manifolds, were measured. The crystal-field splitting schemes for allJ-manifolds which are involved in (J →J′)-luminescence transitions and stimulated emission parameters of Er³⁺ -ions in BaY₂F₈ were determined. A comparison of laser powers and efficiencies of BaY₂F₈ and Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and LiYF₄ single crystals doped with Er³⁺-ions shows the similar performance of these materials.

     

Effect of different doped elements on visible light absorption and ultraviolet light emission on Er3+:Y3Al5O12

In this progress report, seven kinds of novel carefully designed and fabricated up-conversion luminescence agents, Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_nY_3?nAl₅O₁₂, Er³⁺:Y₃B_aAl_5?aO₁₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂, Er³⁺:Y₃Al₅N_xO_12?x, Er³⁺:Y₃Al₅F_yO_12?y and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y, are successfully synthesized using sol–gel methods. After that, their corresponding photocatalysts, Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_nY_3?nAl₅O₁₂/TiO₂, Er³⁺:Y₃B_aAl_5?aO₁₂/TiO₂, Er³⁺:Y₃Ga_bAl_5?bO₁₂/TiO₂, Er³⁺:Y₃Al₅N_xO_12?x/TiO₂, Er³⁺:Y₃Al₅F_yO_12?y/TiO₂ and Er³⁺:Yb_nY_3?nB_aGa_bAl_5?a?bN_xF_yO_12?x?y/TiO₂, are also prepared by sol–gel coating process. The obtained up-conversion luminescence agents and photocatalysts were characterized by using XRD, XPS, SEM, UV–vis and fluorescence spectrophotometer. Synchronously, several kinds of organic dyes are used to test their photocatalytic degradation using prepared photocatalysts. It indicates that the up-conversion luminescence ability of Er³⁺:Y₃Al₅O₁₂ can be improved obviously through doping of some elements. And then, the photocatalytic activity of TiO₂ is markedly enhanced by modified up-conversion luminescence agents which can transform much visible light into ultraviolet light.     

Physical and Spectral Investigations of Cu<Superscript>2+</Superscript>-Doped Alkali Zinc Borate Glasses

Physical and spectral studies on 20ZnO + xLi₂O + (30-x)Na₂O + 50B₂O₃ (5 ≤ x ≥ 25) doped with 0.1 mol% of paramagnetic CuO impurity are carried out. Powder X-ray diffraction patterns of the glass samples confirm the amorphous nature. The physical parameters of all the glasses were also evaluated with respect to the composition. The electron paramagnetic resonance spectra of all these glasses exhibit resonance signals that are characteristic of Cu²⁺ ions. The optical absorption spectra also confirm the Cu²⁺ ion in tetragonally elongated octahedral site. Various crystal field, spin-Hamiltonian and bonding parameters are evaluated. It is observed that the mixed alkali effect is significant.     

Spectroscopic and laser properties of Er3+-doped monoclinic BaY2F8 single crystals

The luminescence and absorption properties of Ba(Y_1–x Er _x )₂F₈ (x=0.001, 0.01, 0.05, 0.1, 0.2 and 0.3) and the Er³⁺-ion decay kinetics of luminescent transitions from three initial laser states, the⁴S_3/2,⁴F._9/2 and⁴I_11/2 manifolds, were measured. The crystal-field splitting schemes for allJ-manifolds which are involved in (J J)-luminescence transitions and stimulated emission parameters of Er³⁺ -ions in BaY₂F₈ were determined. A comparison of laser powers and efficiencies of BaY₂F₈ and Y₃Al₅O₁₂, Lu₃Al₅O₁₂ and LiYF₄ single crystals doped with Er³⁺-ions shows the similar performance of these materials.     

Luminescence of excitons in single-crystal garnets

Comparative studies of the luminescence of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and their volume analogues—Y₃Al₅O₁₂ and Y₃Al₅O₁₂:Ce single crystals, excited by synchrotron radiation with energy E=120–150 eV, have been performed. The films were grown from melt-solution by liquid-phase epitaxy and the crystals were grown from melt. The single-crystal films and single crystals studied are characterized by different degrees of structural order, in particular, different concentrations of substitutional defects of the Y _Al ³⁺ and LU _Al ³⁺ types. It was ascertained that the bands at 260 and 250 nm in the intrinsic luminescence spectra of Y₃Al₅O₁₂:Ce and Lu₃Al₅O₁₂:Ce single-crystal films and single crystals are due to the emission of self-trapped excitons. The luminescence band with λ_max=300 nm and τ=0.36 μs, which is present in the luminescence spectrum of single crystals and absent in the spectra of single-crystal films, is due to the recombination of electrons with holes localized at Y _Al ³⁺ centers. It is shown that an efficient energy transfer by excitons to activator ions occurs in Y₃Al₅O₁₂ and Lu₃Al₅O₂ single-crystal films doped with Ce³⁺ ions.     

Improvement of sonocatalytic activity of TiO2 by using Yb,N and F-doped Er3+:Y3Al5O12 for degradation of organic dyes

In this study, several up-conversion luminescence agents (Er³⁺:Y₃Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99 and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98) were synthesized using sol–gel method. And then, the corresponding sonocatalyst (Er³⁺:Y₃Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅O₁₂/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01O_11.99/TiO₂, Er³⁺:Yb_0.2Y_2.79Al₅F_0.01O_11.99/TiO₂ and Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites) were prepared by sol–gel coating process. The synthesized up-conversion luminescence agents and their coated composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). And that, the sonocatalytic activities were detected through the degradation of Azo Fuchsine (AF) dye in aqueous solution by UV–vis spectroscopy. Some key influences such as heat-treated temperature and heat-treated time on the sonocatalytic activity of Er³⁺:Yb_aY_2.99−aN_xF_yAl₅O_12−x−y/TiO₂ coated composite, as well as ultrasonic irradiation time and initial dye concentration on the sonocatalytic degradation were studied. The results showed that the doping of Yb, N and F into Er³⁺:Y₃Al₅O₁₂/TiO₂ significantly enhanced the sonocatalytic activity of Er³⁺:Y₃Al₅O₁₂/TiO₂ coated composite in the degradation of organic dyes. Particularly, Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites with 3:7 M ratio heat-treated at 550 °C for 60 min showed the highest sonocatalytic activity. At last, the experiments also indicated that the Er³⁺:Yb_0.2Y_2.79Al₅N_0.01F_0.01O_11.98/TiO₂ coated composites has a good sonocatalytic activity to degrade other organic dyes under ultrasonic irradiation.     

Preparation, Luminescence Properties, and Application of Scintillators Based on Lu3Al5O12:Ce Single‐Crystal Films

The possibility of obtaining scintillators with a high effective atomic number of the element Z _ef based on Lu₃Al₅O₁₂:Ce³⁺ singlecrystal films (SCF) on doping with La³⁺ and Sc³⁺ ions on Y₃Al₅O₁₂ substrates has been investigated. It is established that the SCF of (LuLaY)₃Al₅O₁₂:Ce³⁺ (Z _ef = 58.9 and = 6.67 g/cm²) does not rank below those of Y₃Al₅O₁₂:Ce³⁺ (Z _ef = 29 and = 4.52 g/cm²) in the conversion efficiency of radiation at the band with _max = 515 nm. This allows their use as screens of xray images with a space resolution of 0.75–1.00 m. It is suggested that in the SCF of Lu₃Al₅O₁₂ the isoelectronic impurities of lanthanum and scandium form radiative recombination centers of the type La_Lu, Sc_Lu, and ScAl as well as the centers Lu as a consequence of the effect of replacement of some Lu³⁺ ions by the La³⁺ ions to octanodes of the garnet lattice. The low efficiency of Ce³⁺ radiation in the SCF of (LuSc)₃(AlSc)₅O₁₂:Ce is explained by substantial losses due to excitation of the recombination luminescence in the UV region of the centers formed by the isoelectronic impurities of scandium and to the possible existence of the channel of energy excitation dissipation related to the transitions between extrema of the allowed energy bands and activator levels.     

Spin states of Ni3+ ions in PrSrAl1−x Ni x O4 ceramics

Solid solutions PrSrAl_1−x Ni _x O₄ have been synthesized and studied by electron paramagnetic resonance (EPR). It is shown that atx≤0.2 the Ni³⁺ ions may be present both in the high- and low-spin states. Asx increases, the part of high-spin centers increases as well. Models of the paramagnetic centers accounting for micro-heterogeneous structure of these ceramics are proposed. The observed features of the temperature dependence of the EPR signals are explained by the interaction of the nickel ions with fast-relaxing Pr³⁺ ions.     

Thermoluminescence and thermal properties of rare-earth-ion-activated YAG crystals

The paper contains results of studies of repeated thermoluminescence of yttrium-aluminum garnet (YAG) crystals (Y_3−xLn_xAl₅O₁₂, x=0, 2) activated by rare earth ions (Pr³⁺, Nd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺) previously exposed to⁶⁰Co γ-radiation at 77 K and subjected to many cooling-heating cycles. A possible mechanism of repeated thermoluminescence is considered from the viewpoint of a dynamic evolutionary approach. The thermal conductivity of YAG-TR³⁺ crystals (TR³⁺: Gd³⁺, Tb³⁺, Dy³⁺, Er³⁺, Tm³⁺, and Lu³⁺) is studied to establish its relation with repeated thermoluminescence. Presented at the National Conference on Molecular Spectroscopy, Samarkand (Uzbekistan), September 25–27, 1996. Samarkand State University, 15, University Blvd., 703004, Samarkand, Republic of Uzbekistan. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 1, pp. 137–140, January–February, 1998.     

Up-conversion emissions of Er<Superscript>3+</Superscript>-Yb<Superscript>3+</Superscript> codoped Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by the arc discharge synthesis method

The Er³⁺-Yb³⁺ codoped Al₂O₃ nanoparticles with an average particle size of about 50 nm have been synthesized by an arc discharge synthesis method. The green and red up-conversion emissions centered at about 526, 547 and 677 nm, corresponding respectively to the ²H_11/2→⁴I_15/2, ⁴S_3/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2 transitions of Er³⁺, were detected by a 978-nm semiconductor laser diode excitation. The Annealing has evident effect on the up-conversion emissions of the samples: The red up-conversion emission is noticeable before annealing; however, the green up-conversion emission becomes predominant after annealing. The mixture of (Er,Yb)₃Al₅O₁₂ and α-(Al,Er,Yb)₂O₃ phases is more favorable for green up-conversion emissions due to an enhancement of the ESA (I) of ⁴I_11/2+a photon→⁴F_7/2 and ET (III) of ²F_5/2(Yb³⁺)+⁴I_11/2(Er³⁺)→²F_7/2(Yb³⁺)+⁴F_7/2(Er³⁺) processes. The two-photon absorption up-conversion process is involved in the green and red up-conversion emissions. The results have proved that arc discharge synthesis is a new promising preparation technology for optical materials. Supported by National Natural Science Foundation of China (Grant No. 10804015), the Scientific Research Foundation for Doctor of Liaoning Province (Grant No. 20071095), and the Educational Committee Foundation of Liaoning Province (Grant No. 2008123)     

Enhanced optical activation of Er in Er-doped Al2O3 powders by Y codoping in a sol-gel method

Enhanced photoluminescence (PL) mechanism of Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping at wavelength 1.53 μm has been investigated through PL measurements of 0.1 mol% Er³⁺- and 0-20 mol% Y³⁺-codoped Al₂O₃ powders prepared at a sintering temperature of 900 °C in a non-aqueous sol-gel method. PL intensity and lifetime of Er³⁺-Y³⁺-codoped Al₂O₃ powders composed of γ-(Al,Er,Y)₂O₃ and θ-(Al,Er,Y)₂O₃ phases increased with increasing Y³⁺-codoping concentration. The 10-20 mol% Y³⁺ codoping in 0.1 mol% Er³⁺-doped Al₂O₃ powders intensified the PL intensity by about 20 times, with a PL lifetime prolonged from 3.5 to 5.8 ms. A maximal increase of the optical activity of Er³⁺ in 0.1 mol% Er³⁺-Y³⁺-codoped Al₂O₃ powders about one order was achieved by 10-20 mol% Y³⁺ codoping. It is found that the improved PL properties for Er³⁺-Y³⁺-codoped Al₂O₃ powders are mainly attributed to enhanced optical activation of Er³⁺ in the Al₂O₃ by Y³⁺ codoping, and to the slightly increased radiative quantum efficiency of Er³⁺ in the Al₂O₃.     

Synthesis and luminescence properties of Er3+-doped Lu3Ga5O12 nanocrystals

The concentration-dependent luminescence properties of sol–gel-derived nanocrystalline Lu_3(1?x)Er_3xGa₅O₁₂ powders (where x=0.01, 0.05 and 0.1) have been studied. Laser-excited luminescence spectra, emission decays and upconversion luminescence of Er³⁺-doped Lu₃Ga₅O₁₂ nanocrystalline samples have been measured. The decay curve of the (²H_11/2,⁴S_3/2) emission exhibits a non-exponential behavior presumably due to cross-relaxation process. Moreover, near-infrared to visible upconversion luminescence has been observed in the green region for 1.0 mol% Er³⁺ ions in Lu₃Ga₅O₁₂ nanocrystals upon 815 nm excitation. The power dependence of the anti-Stokes luminescence suggests that upconversion is probably achieved through the sequential absorption of two photons. To the best of our knowledge, this is the first report on the preparation and optical properties of Er³⁺-doped Lu₃Ga₅O₁₂ in the form of nanocrystalline powders.     

Magnetothermal properties of Gd<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Y<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript>2</Subscript> compounds

The heat capacity of pseudobinary intermetallic compounds Gd_1−x Y _x Ni₂ (0≤x≤1) has been studied. The magnetic contribution to the total heat capacity is isolated with the use of the data obtained for the paramagnetic analogs Lu_1−y Y _y Ni₂ possessing the same molar masses as the gadolinium compounds. It has been found that the difference between the entropies of the Gd_1−x Y _x Ni₂ (x<0.8) compounds and the corresponding paramagnetic Lu_1−y Y _y Ni₂ analogs reaches larger values than those expected from the calculations performed under the assumption that only Gd ions contribute to the magnetic part of the total entropy. The existence of an additional contribution of magnetic nature to the entropy of the Gd_1−x Y _x Ni₂ compounds, as well as the large values of the γ coefficient in the linear-in-temperature term of the heat capacity, is assigned to the spin fluctuations induced by the f—d exchange in the subsystem of Ni 3d electrons.     

Room temperature magnetization measurements of some substituted rare earth iron garnets

The saturation magnetization (M _s) and the initial magnetic susceptibility (χ _in) of substituted yttrium iron garnet (YIG) Ho_3−x Y _x Fe₅O₁₂ where (x=0,0.3,1.5), pure terbium iron garnet Tb₃Fe₅O₁₂, and substituted aluminum iron garnet (AlIG) Ho₃Fe_5−x Al _x O₁₂ where (x=0.05,0.7) at room temperature are reported. It has been observed that M _s and χ _in decrease in a linear manner as Ho³⁺ replaces Y³⁺ in yttrium iron garnet. For substituted (AlIG), a drastic decrease in both M _s and χ _in as Al³⁺ ions replace Fe³⁺ ions. The rate of decrease of M _s and χ _in with the increase of Al³⁺ for substituted (AlIG) is greater than that for substituted (YIG). That is attributed to the decrease in the superexchange interaction (self and mutual iron interactions) with Al substitution.     

Orthorhombic centers of rare-earth <Emphasis Type="Italic">S</Emphasis>-ions in lutetium–aluminum garnet crystals

Electron paramagnetic resonance spectra of Eu²⁺ and Gd³⁺ centers in Lu₃Al₅O₁₂ single crystals have been studied and the parameters of their rhombic spin Hamiltonian have been determined.