Obtention par trempe a partir de l'etat liquide d'une nouvelle phase dans le systeme Nd2O3.Al2O3. etude comparative avec Nd4Ga2O9

By using splat cooling devices associated with laboratory solar furnace a new phase is obtained in the neodymium rich part of the Al₂O₃Nd₂O₃ system. X ray and optical absorption studies and comparisons with Nd₄Ga₂O₉ show that the two phases are isostructural and monoclinic (space group P_21/C) with Al³⁺ in tetrahedral coordination. Optical examinations show that substitution of Al³⁺ by Si⁴⁺ induced a disorder on the neodymium site.     

Novel upconversion phenomenon of Nd sensitized by Yb in Nd-Yb-co-doped β-Na(Y1.5Na0.5)F6

Hexagonal phase Na(Y_1.5Na_0.5)F₆ co-doped with Yb³⁺ and Nd³⁺ was synthesized and its structure was studied by XRD and Raman methods. The Raman scattering spectrum illustrates it is a host with low phonon energy. Emissions in green (⁴G_7/2 → ⁴I_9/2), yellow (⁴G_7/2 → ⁴I_11/2), red (⁴G_7/2 → ⁴I_13/2), and infrared (⁴F_5/2 → ⁴I_9/2, ⁴F_3/2 → ⁴I_9/2) were observed and were the direct result of emissions of the Nd³⁺ ion. The luminescence intensity ratio (I₈₆₃/I₈₀₄) gradually decreased with the increase of excitation power. The long lifetime of 863 nm infrared emission was proved. The upconversion mechanism was deduced to be energy transfer from the Yb³⁺ to Nd³⁺ under 980 nm excitation, by analyzing the energy level structures of Nd³⁺ and Yb³⁺ ions and measuring the power dependence of upconverted emission intensities.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

Concentration effect of Nd ion on the spectroscopic properties of Er/Nd co-doped LiYF4 single crystal

High quality Er³⁺/Nd³⁺:LiYF₄ single crystals were grown by a Bridgman method. Their spectroscopic properties were studied to understand the Nd³⁺ concentration effect upon excitation of an 800 nm laser diode. The intensest 2.7 μm emission was observed in the LiYF₄ crystal codoped with 0.99 mol% Er³⁺ and 0.62 mol% Nd³⁺. Meanwhile, the emission intensity for the green up-conversion and 1.5 μm downconversion of Er³⁺ decreased with increasing of the Nd³⁺ concentration. The modified Inokuti–Hirayama model was used to analyze the decay curves of the 1.06 (Nd³⁺) and 1.5 (Er³⁺) μm emissions. The results indicated that the energy transfer process (Er³⁺:⁴I_13/2 + Nd³⁺:⁴I_9/2 → Er³⁺:⁴I_15/2 + Nd³⁺:⁴I_15/2) is mainly due to the electric dipole–dipole interaction. The energy transfer efficiencies between Nd³⁺ and Er³⁺ ions were calculated. All results suggested that the Er³⁺/Nd³⁺:LiYF₄ single crystals may have potential applications in mid-infrared lasers.     

Effect of Al2O3 concentration on zirconolite (Ca(Zr,Hf)Ti2O7) crystallization in (TiO2,ZrO2,HfO2)-rich SiO2–Al2O3–CaO–Na2O glasses

Glass-ceramic matrices containing zirconolite (nominally Ca(Zr,Hf)Ti₂O₇) crystals in their bulk that would incorporate high proportions of minor actinides (Np, Am, Cm) or plutonium could be envisaged for their immobilization. Zirconolite-based glass-ceramics can be prepared by controlled crystallization of zirconolite in glasses belonging to SiO₂–Al₂O₃–CaO–Na₂O–TiO₂–ZrO₂–HfO₂ system. In this study, neodymium was used as trivalent actinides surrogate. Increasing Al₂O₃ concentration in glass composition had a strong effect on the nucleation rate I _z of zirconolite crystals in the bulk, on the amount of neodymium incorporated in zirconolite phase and on the crystal growth rate of silicate phases (titanite + anorthite) from glass surface. These results could be explained by the existence of competition—in favor of aluminum—between Al³⁺ and (Ti⁴⁺, Zr⁴⁺, Hf⁴⁺) ions for their association with charge compensators cations to facilitate their incorporation in the glassy network. Differential thermal analysis (DTA) was used to study exothermal effects associated with bulk and surface crystallization. ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR) spectra showed that aluminum enters glasses network predominantly in 4-fold coordination. Neodymium optical absorption and fluorescence spectroscopies showed that the Al₂O₃ concentration changes performed in this study had not significant effect on Nd³⁺ ions environment in glasses.     

Susceptibilite paramagnetique anisotrope de monocristaux d'oxyds Nd2O3 et LaxNd2−xO3

Single crystals of neodymium oxide Nd₂O₃ and of a solid solution La_{0, 4}Nd_{1, 6}O₃ both with hexagonal A structure were obtained by Verneuil process adapted to plasma torch. Paramagnetic susceptibilities measurements were performed on these crystals at constant temperatures (5, 77 and 300 K) with various orientations of the magnetic field with regard to crystallographic axes. The curves are of the type X = A + B cos 2 θ. Variations of susceptibility versus temperature in the range 5–300 K clearly show an anisotropy. The perpendicular susceptibility varies roughly according to a Curie-Weiss law, whereas the variation of parallel susceptibility may be explained by an evolution of Nd³⁺ magnetic moment due to crystal field at low temperatures.     

The effect of In ion on the optical characteristics of Er in Er/Yb:LiNbO3 crystal

The effect of In³⁺ ion on the optical characteristics of Er³⁺ ion in Er/Yb:LiNbO₃ crystal under 980 nm excitation has been investigated. The Er and Yb contents in the crystals were measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES). A significant enhancement of 1.54 μm emission was observed for Er/Yb:LiNbO₃ crystal doped with 1 mol% In₂O₃. The studies on the UV-vis absorption and the OH⁻ absorption spectra indicate that the threshold concentration of In³⁺ ion decreases with the Er/Yb doping in Er/Yb/In:LiNbO₃ crystal. The 1 mol% In₂O₃ doping results in the reduction of absorption cross section in the UV-vis region, meaning the formation of Er³⁺ cluster sites. The enhancement of 1.54 μm emission is attributed to the larger probabilities of the cross relaxation processes ⁴S_3/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2 (Er), ⁴S_3/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_9/2 (Er) and ⁴I_9/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_13/2 (Er) induced by Er³⁺ cluster sites.     

Efficient Bi → Nd energy transfer in Gd2O3:Bi,Nd

Bi³⁺,Nd³⁺ co-doped Gd₂O₃ were prepared by solid state reaction and the optical properties were investigated. The results show that the near-infrared emission of Nd³⁺ ions is significantly enhanced by the introducing of Bi³⁺ in co-doped samples. An efficient energy transfer from Bi³⁺ to Nd³⁺ corresponds to the near-infrared emission enhancement. The energy transfer efficiency reaches 64.1% for the sample with the strongest near-infrared emission, which has the optimized doping concentrations of 0.5% for Bi³⁺ and 2% for Nd³⁺. The interesting optical properties make Bi³⁺,Nd³⁺ co-doped Gd₂O₃ promising as the luminescent down-conversion layers in front of c-Si solar cells to enhance the performance of the solar cells.     

Polarized spectroscopic properties of Ho ions in NaLa(MoO4)2 crystal

A Ho³⁺-doped NaLa(MoO₄)₂ single crystal was grown by the Czochralski method. The polarized absorption spectra, polarized fluorescence spectra, and fluorescence decay curves of the crystal were measured at room temperature. The spontaneous emission probabilities, radiative lifetimes, and fluorescence branching ratios of the typical fluorescence multiplets of Ho³⁺ ions were calculated. The polarized stimulated emission and gain cross-sections of the ⁵I₇ → ⁵I₈ transition were obtained. The results show that the Ho³⁺:NaLa(MoO₄)₂ crystal is a promising gain medium for tunable and ultrashort pulse lasers operating around 2.0 μm.     

Upconversion in Er-doped Gd2O3 nanocrystals prepared by propellant synthesis and flame spray pyrolysis

In this study, monoclinic luminescent Gd₂O₃ nanocrystals doped with different concentrations of Er³⁺ (0.1, 1, and 10 mol%) were produced by propellant synthesis and flame spray pyrolysis (FSP). A comparison of their optical and morphological properties is reported. Following 980 nm excitation, an increase of the emission intensity from the ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions was observed with increasing Er³⁺ concentration in the Gd₂O₃ nanocrystalline samples prepared via both techniques. However, the overall upconversion emission intensity was greater for the samples obtained by FSP. Furthermore, as the Er³⁺ concentration was increased, the intensity of the red (⁴F_9/2 → ⁴I_15/2) emission was observed to increase more rapidly in comparison to the green (²H_11/2, ⁴S_3/2 → ⁴I_15/2) emission resulting in an overall enhancement of the red component in the upconversion emission. Although both synthetic routes yield average crystallite sizes in the nanoscale, the TEM and SEM images confirm a more homogeneous morphology and lower particle aggregation for the nanocrystals produced by FSP.     

High pressure luminescence and time resolved spectra of La2Be2O5:Pr

We present luminescence, luminescence excitation and luminescence time resolved spectra of La₂Be₂O₅:Pr³⁺ system. We used high pressure spectroscopy approaches, with high pressure applied in diamond anvil cell (DAC) and sapphire anvil cell (SAC), for detailed analysis of luminescence related to the 4f5d → 4f² and 4f² → 4f² transitions. We present effect of up-converted luminescence related to 4f5d → 4f² transition excited with 488 nm. We also discussed possibility of existence of praseodymium trapped exciton (PTE) states in La₂Be₂O₅:Pr³⁺ system. Lack of the PTE is attributed to high quantity of bulk modulus of this material.     

Crystal growth and scintillation properties of Nd-doped Lu3Al5O12 single crystals with different Nd concentrations

Nd 0.1%, 0.5%, 1% and 3% doped Lu₃Al₅O₁₂ (Nd:LuAG) single crystals were grown in the nitrogen atmosphere by the micro-pulling down (μ-PD) method. The grown crystals had a single-phase confirmed by powder XRD analysis. In absorption spectra, some weak absorption lines due to Nd³⁺ 4f-4f transitions were observed and their intensity increased with the increase of Nd concentration. When excited by ²⁴¹Am α-ray, a broad emission peak due to defects in the host lattice at 320 nm and some sharp lines due to Nd³⁺ 4f-4f transitions at wavelength longer than 400 nm were observed. The decay time profiles of Nd:LuAG under γ-ray excitation were well approximated by two exponential function of 340-760 ns and 3-5 μs for each sample. By pulse height measurement using ¹³⁷Cs, Nd 0.5%:LuAG showed the highest light yield of 7600 ± 760 photons/MeV.     

Optical properties of transparent Dy doped Ba2TiSi2O8 glass ceramic

The Ba₂TiSi₂O₈ is a well known piezoelectric, ferroelectric and non-linear crystal. Nanocrystals of Ba₂TiSi₂O₈ doped with 1.5 Dy³⁺ have been obtained by thermal treatment of a precursor glass and their optical properties have been studied. X-ray diffraction patterns and optical measurements have been carried out on the precursor glass and glass ceramic samples. The emission spectra corresponding to the Dy³⁺: ⁴F_9/2 → ⁶H_13/2 (575 nm), ⁴F_9/2 → ⁶H_11/2 (670 nm) and ⁴F_9/2 → ⁶H_9/2 (757 nm) transitions have been obtained under laser excitation at 473 nm. These measurements confirm the incorporation of the Dy³⁺ ions into the Ba₂TiSi₂O₈ nanocrystals which produces an enhancement of luminescence at 575 nm. At this wavelength has been demonstrated a maximum optical amplification around 1.9 cm⁻¹ (∼8.2 dB/cm).     

Luminescence properties of Nd-doped (Y,Gd)BO3 phosphors

A system of 0.03 mol Nd³⁺-doped (Y,Gd)BO₃ phosphors were prepared by the conventional solid state reaction method for different concentrations of Gd³⁺ ions and were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and NIR emission measurements. The emitted radiation was dominated by 1057 nm peak in the NIR region as a result of ⁴F_3/2 → ⁴I_11/2 transitions of Nd³⁺ ions. As the concentration of Gd³⁺ ions increases from 0.00 to 0.57 mol, the grain sizes and the intensity of NIR emission peaks were improved. The results are discussed in comparison with similar reported works.     

Hydrothermal synthesis and luminescence properties of octahedral LiYbF4: Er microcrystals

LiYbF₄: Er³⁺ octahedral microcrystals have been successfully prepared through a facile hydrothermal method assisted with EDTA (ethylenediaminetetraacetic acid). X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric and differential scanning calorimeters (TG-DSC), photoluminescence (PL) spectra are used to characterize the samples. Under 976 nm excitation, the upconversion (UC) luminescence emission spectra of LiYbF₄: Er³⁺ microcrystals show the characteristic Er³⁺ emissions. The results show that the infrared light emissions at 792 nm of ⁴I_9/2 → ⁴I_15/2 are dominantly strong unusually, while the green emissions at 526 and 545 nm assigned to ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2, respectively, and the red emission at 667 nm of ⁴F_9/2→⁴I_15/2 are relatively weaker. Most importantly, the samples show more efficient luminescence with further heat treatment.     

Splitting and broadening of the emission bands of Y2O3:Eu3+,Nd3+ and its dependence on Nd3+ concentration and annealing temperature

Although Eu³⁺ ion-doped Y₂O₃ has been extensively used as red phosphors, their color rendering needs to be improved for high-quality illumination and displaying. Here, we show that the emission spectra of Y₂O₃:Eu³⁺ red phosphors can be broadened by the doping of Nd³⁺ ion so that the color rendering capability of Y₂O₃:Eu³⁺ was remarkably enhanced. Y₂O₃:Eu³⁺ and Y₂O₃:Eu³⁺,Nd³⁺ colloidal spheres were synthesized by wet chemical procedure and high-temperature treatment. The fluorescence measurement under the 254 and 380 nm ultraviolet excitation indicates that the 612 nm red emission peak of Eu³⁺ can be splitted into two ones by the doping of Nd³⁺ ion, of which the full width at half maximum (FWHM) is broadened from 4.2 nm to 9.6 nm. By varying the concentration of Nd³⁺ ion, it was determined that the optimal doping concentration of Nd³⁺ ion is of 3 mol% for realizing the strongest emission intensity. The further increase of Nd³⁺ ion exceeding 3 mol% would lead to a concentration quenching phenomenon. The analysis based on XRD spectra and the simplified energy diagram suggested that the doped Nd³⁺ ion not only monitored the growth dynamics, but also took an efficient energy transfer and a cross relaxation process to generate intense emission from Eu³⁺ ion in both of C₂ and S₆ sites, instead of preferable one type of Eu³⁺ site (C₂ or S₆) in the Nd³⁺ undoped sample.     

Effect of Y3+ codoping on luminescence decays of the 4I13/2 level in Er3+-doped Al2O3 powders prepared by a sol-gel method

The luminescence lifetime of the 0.01 mol.%-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 has been investigated to explore the enhanced mechanism of photoluminescence properties of the Er³⁺-doped Al₂O₃ by Y³⁺ codoping. For the 0.1 mol.% Er³⁺-Y³⁺-codoped Al₂O₃ powders, the measured lifetime of Er³⁺ gradually increases with increasing Y³⁺ concentration. Consequently, codoping with 20 mol.% Y³⁺ leads to an increase in the measured lifetime from 3.5 to 5.8 ms. By comparing the measured lifetime for different Er³⁺ concentrations in the Al₂O₃ powders, the radiative lifetime of both the Er³⁺-doped and the Er³⁺-Y³⁺-codoped Al₂O₃ powders is estimated to be about 7.5 ms. Infrared absorption spectra indicate that Y³⁺ codoping does not change the-OH content in the Er³⁺-Y³⁺-codoped Al₂O₃ powders. The prolonged luminescence lifetime of the ⁴I_13/2 level of Er³⁺ in Er³⁺-doped Al₂O₃ powders by Y³⁺ codoping is ascribed to the decrease in the energy transfer rate between the Er³⁺ ions and the Er³⁺ and -OH, respectively, due to the suppressed interaction between Er³⁺ ions.     

White upconverted luminescence of Ho/Yb/Tm tri-doped Gd2Mo3O9 phosphors

Yb³⁺/Tm³⁺/Ho³⁺ tri-doped Gd₂Mo₃O₉ phosphors were synthesized by the high-temperature solid-state method. Under 980 nm near-infrared excitation, the white-light emission can be observed, which is consists of the blue, green, and red UC emissions. The green and red emission at 547 nm and 660 nm originated from the transition of Ho³⁺ (⁵S₂, ⁵F₄ → ⁵I₈ and ⁵F₅ → ⁵I₈) and the blue emission at 475 nm attributed to the transition of Tm³⁺ (⁵G₄ → ⁵H₆). In this experiment, we selected the optimum concentration ratio of the three rare earths for the bright white emission. The Commission internationale de L’Eclairage (CIE) coordinates for the samples were calculated, and chromaticity coordinates were very close to white light regions. We find that the calculated CIE color coordinates of the Yb³⁺/Tm³⁺/Ho³⁺ tri-doped Gd₂Mo₃O₉ phosphors changed with the incident pump power from 400 mW/cm² to 1000 mW/cm². The upconversion luminescence mechanism of the samples was discussed on its spectral. The white light may be proved to be a candidate material for applications in various fields.     

Synthesis and upconversion luminescence properties of Yb/Er codoped BaGd2(MoO4)4 powder

Synthesis and upconversion luminescence properties of the new BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor were reported in this paper. The phosphor powder was obtained by the traditional high temperature solid-state method, and its phase structure was characterized by the XRD pattern. Based on the upconversion luminescence properties studies, it is found that, under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits intense green upconversion luminescence, which is ascribed to ²H_11/2 → ⁴I_15/2 and ⁴S_3/2 → ⁴I_15/2 transition of Er³⁺. While the observed much weaker red emission is due to the non-radiative relaxation process of ⁴S_3/2 → ⁴F_9/2 and ⁴F_9/2 → ⁴I_15/2 transition originating from the same Er³⁺. The concentration quenching effects for both Yb³⁺ and Er³⁺ were found, and the optimum doping concentrations of 0.5 mol% Yb³⁺ and 0.08 mol% Er³⁺ in the new BaGd₂(MoO₄)₄ Gd³⁺ host were established.     

Synthesis and spectral properties of colloidal Nd doped NaYF4 nanocrystals

Transparent, chloroform dispersed α-NaYF₄ nanocrystals doped with neodymium ions were synthesized and characterized. XRD and TEM measurement confirmed cubic structure of α-NaYF₄ of the nanoparticles (NPs). The absorption and emission spectra as well as ⁴F_3/2 level fluorescence decay curves were measured in order to estimate the influence of Nd³⁺ concentration in the matrix on the optical properties of the NPs. With the increase of Nd³⁺ doping level, the Judd-Ofelt Ω₄ parameter as well as the spectroscopic Nd³⁺ parameter X_Nd = Ω₄/Ω₆ was growing. In the same time the Ω₂ and Ω₆ were decreasing. Theoretical luminescence lifetimes of the ⁴F_3/2 level equal to ∼300 μs were also calculated and compared with the experimental values to quantify the concentration quenching. Based on this comparison, quantum efficiency was found to vary systematically between ∼100% and 4% for Nd³⁺ content increasing from 2 up to 25%.