Upconversion Luminescence of Gd<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> Ions

The upconversion luminescence (UCL) of nanocrystalline gadolinium oxide (Gd₂O₃) doped with Er³⁺ and Yb³⁺ ions has been studied in the temperature range of 90–400 K. The nanocrystals were synthesized by chemical vapor deposition and possessed a cubic crystalline structure with an average particle size within 48–57 nm. It is established that the USL intensity in the red (⁴F_9/2 → ⁴I_15/2 transition in Er3+ ion) and green (⁴S_3/2 → ⁴I_15/2 transition) spectral regions depends on the sample temperature and concentration of dopant ions, as well as on the additional structural defects (anion vacancies) created in the crystal lattice by the introduction of Zn²⁺ ions or irradiation with high-energy (10 MeV) electrons. The luminescence efficiency and spectrum of the upconversion phosphor are determined by energy transfer processes.     

Luminescence studies on Eu<Superscript>2+</Superscript> and Tb<Superscript>3+</Superscript> doped Ca<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript> phosphors

Eu²⁺ and Tb³⁺ doped Ca₂MgSi₂O₇ phosphors were synthesized by conventional solid-state reaction. The phase formation was confirmed by X-ray powder diffraction technique and refined lattice parameters were calculated by rietveld refinement process using Celref v3. The photoluminescence (PL) excitation and emission spectra were investigated. The phosphors exhibited broaden green emitting luminescence peaking at 520 nm when excited at 374 nm source. Morphological studies were carried out using Scanning electron microscopy (SEM) images of the sample with optimum PL emission. The dependence of photoluminescence intensity on co-dopant concentration and the kinetic parameters were also reported. Time resolved fluorescence spectroscopy (TRFS) is used to investigate the decay in luminescence signals with respect to time. The sample proved to be a good long lasting material, which makes it useful in emergency signs, textile printing, textile exit sign boards and electronic instrument dial pads etc.     

Synthesis of Er<Superscript>3+</Superscript> and Er<Superscript>3+</Superscript> : Yb<Subscript>3+</Subscript> doped sol-gel derived silica glass and studies on their optical properties

Er₃₊ and Er₃₊ : Yb₃₊ doped optical quality, crack and bubble free glasses for possible use in making laser material have been prepared successfully through sol-gel route. The thermal and optical, including UV-visible absorption, FTIR etc characterizations were undertaken on the samples. The absorption characteristics of Er₃₊ doped samples clearly revealed the absorption due to Er₃₊ ions. On the other hand Yb₃₊ : Er₃₊ doped samples showed enhanced absorption due to² F _7/2 →² F _5/2 transition. The absorption and emission cross-section for² F _7/2 ↔² F _5/2 of Yb³⁺ were estimated. FTIR absorption spectra have clearly shown the reduction of the absorption peak intensity with heat treatment in the range 3700–2900 cm⁻¹. The 960 cm^-1 band also showed progressive decrease in the absorption band peak intensity with heat treatment. The result of the investigations with essential discussions and conclusions have been reported in this paper.     

Synthesis and photoluminescence study of narrow-band UVB-emitting LiSr<Subscript>4</Subscript>(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Gd<Superscript>3+</Superscript>, Pr<Superscript>3+</Superscript> phosphor

A series of Pr³⁺, Gd³⁺ and Pr³⁺–Gd³⁺-doped inorganic borate phosphors LiSr₄(BO₃)₃ were successfully synthesized by a modified solid-state diffusion method. The crystal structures and the phase purities of samples were characterized by powder X-ray diffraction. Surface morphology of the sample was studied by scanning electronic microscopy (SEM). The optimal concentrations of dopant Gd³⁺ ions in compound LiSr₄(BO₃)₃ were determined through the measurements of photoluminescence (PL) spectra of phosphors. Gd³⁺-doped phosphors LiSr₄(BO₃)₃ show strong band absorption in UV spectral region and narrow-band UVB emission under the excitation of 276 nm was only due to ⁶P _J → ⁸S_7/2 transition of Gd³⁺ ions. The effect of Pr³⁺ ion on excitation of LiSr₄(BO₃)₃:Gd³⁺ was also studied. The excitation of LiSr₄(BO₃)₃:Gd³⁺, Pr³⁺ gives a broad-band spectra, which show very good overlap with the Hg 253.7 nm line. The photoluminescence spectra of LiSr₄(BO₃)₃ with different doping concentrations Pr³⁺ and keeping the concentration of Gd³⁺ constant at 0.03 mol have also been studied. The emission intensity of LiSr₄(BO₃)₃:Pr³⁺–Gd³⁺ phosphors increases with increasing Pr³⁺ doping concentration and reaches a maximum at 0.01 mol. From the photoluminescence study of LiSr₄(BO₃)₃:Gd³⁺, Pr³⁺ we conclude that there was efficient energy transfer from Pr³⁺→ Gd³⁺ ions in LiSr_4?x?y Pr _x Gd _y (BO₃)₃ phosphors.     

Synthesis,structural, photoluminescence and mechanoluminescence properties of Tb<Superscript>3+</Superscript>: Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> novel green nanophosphors

Novel green nanophosphors Ca₂Gd₂W₃O₁₄: Tb³⁺ were synthesized by solid state reaction method. From the X-ray diffraction profiles it is observed that Tb³⁺: Ca₂Gd₂W₃O₁₄ phosphors were crystallized in the form of tetragonal structure. The scanning electron microscopy (SEM) image shows that the particle size is at around 300 nm. In addition to these the prepared powder phosphors were also examined by the energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL) and mechanoluminescence (ML) spectra. Emission spectra of Tb³⁺: Ca₂Gd₂W₃O₁₄ nanophosphors have shown bright green emission at 545 nm (⁵D₄ → ⁷F₅) with an excitation wavelength λ_exci = 374 nm (⁷F₆ → ⁵G₆). ML spectra shows the radiation effect on the Ca₂Gd₂W₃O₁₄: Tb³⁺ nanophosphors and from that it was observed that these phosphors are very less sensitive for lower exposure.     

Synthesis and properties of AgTi<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-based NASICON-type phosphates doped with Nb<Superscript>5+</Superscript>, Zr<Superscript>4+</Superscript>, and Ga<Superscript>3+</Superscript>

We have synthesized materials based on a silver titanium phosphate with partial substitution of tri-, tetra-, or pentavalent cations for titanium: Ag_1±x Ti_2−x M _x (PO₄)₃ (M = Nb⁵⁺, Ga³⁺) and AgTi_2−x Zr _x (PO₄)₃. The materials have been characterized by X-ray diffraction and impedance spectroscopy and have been shown to have small thermal expansion coefficients. Their ionic conductivity has been determined. Silver ions in these materials are difficult to replace with protons.     

Luminescence of BaSiO<Subscript>3</Subscript> crystals doped with Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript>

The Stokes and anti-Stokes luminescence of undoped and rare-earth-doped (Er³⁺ and Yb³⁺) BaSiO₃ has been studied in the temperature range 78–450 K under excitation at 10–1000 mV. The results indicate that the emission mechanism in BaSiO₃ crystals is hole recombination and that the anti-Stokes luminescence is due to consecutive sensitization; that is, the Yb³⁺ ions in the BaSiO₃ compound act as luminescence sensitizers, and the Er³⁺ ions, as activators.     

Spectroscopy and Structure of Nd<Superscript>3+</Superscript> Activator Centers in Stabilized Cubic ZrO<Subscript>2</Subscript>

The nonuniformly broadened spectra of Nd³⁺ in ZrO₂-Y₂O₃-Nd₂O₃ crystals are studied using selective excitation, different time delays, and measurements of the excited-state lifetime at 77 K. Three basic types of optical spectra are identified and are assigned to three basic configurations of the nearest neighbor environment of Nd³⁺: sevenfold coordination and eightfold coordination with and without an oxygen vacancy among its second neighbors.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 8, 2005, pp. 955–959.Original Russian Text Copyright © 2005 by Voron’ko, Lomonova, Popov, Sobol’, Ushakov.     

Combusion synthesis,structural and photo-physical characteristics of Eu<Superscript>2+</Superscript> and Dy<Superscript>3+</Superscript> co-doped SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript> phosphor nanopowders

In this research, we reported the synthesis of Eu²⁺ and Dy³⁺ co-doped SrAl₂O₄ phosphor nanopowders with high brightness and long afterglow by urea-nitrate solution combustion synthesis (SCS) at 600 °C, followed by heating the resultant combustion ash at 1,200 °C in a weak reductive atmosphere (5% H₂ + 95% N₂). The broad-band UV-excited luminescence of the SrAl₂O₄: Eu²⁺, Dy³⁺ nanopowders was observed at λ _max = 517 nm due to transitions from the 4f⁶5d¹ to the 4f⁷ configuration of the emission center (Eu²⁺ ions). The excitation spectra consist of 240- and 254 nm broad peaks. Finally, it was found that the optimum ratio of urea is 2.5 times higher than theoretical quantities for the best emission condition of SrAl₂O₄: Eu²⁺, Dy³⁺ phosphor nanopowders.     

Recombination luminescence of CaI<Subscript>2</Subscript> crystals activated with Eu<Superscript>2+</Superscript>, Gd<Superscript>2+</Superscript>, Tl<Superscript>+</Superscript>, Pb<Superscript>2+</Superscript>, and Mn<Superscript>2+</Superscript>

The spectral characteristics of thermostimulated luminescence, steady-state roentgenoluminescence and photostimulated luminescence (PSL) buildup and decay kinetics, and the effect of IR irradiation on the roentgenoluminescence yield and glow curves of CaI₂:Eu²⁺, CaI₂:Gd²⁺, CaI₂:Tl⁺, CaI₂:Pb²⁺, CaI₂:Mn²⁺, and CaI₂: Pb²⁺, Mn²⁺ crystals grown by the Bridgman-Stockbarger method have been studied in the temperature range 90–295 K. Coupled with earlier data, the present results on the influence of oxygen and hydrogen impurities on the spectral characteristics of CaI₂ indicate that the activation of calcium iodide with Eu²⁺, Gd²⁺, Tl⁺, Pb²⁺, and Mn²⁺ leads to the formation of cation impurity-native defect complexes, which act as carrier traps and are responsible for the thermostimulated luminescence in the range 150–295 K. IR exposure after 90-K x-ray excitation gives rise to flash PSL and influences the thermostimulated luminescence light sum. The nature of the emission and trapping centers involved and the mechanisms of recombination luminescence excitation in the crystals are discussed.     

Synthesis,characterization and formation mechanism of monodispersed Gd<Subscript>2</Subscript>O<Subscript>2</Subscript>S:Eu<Superscript>3+</Superscript> nanocrystals

Monodispersed Gd₂O₂S:Eu³⁺ nanostructures with tunable morphologies have been selectively fabricated by solvothermal method in the presence of stable inorganic precursors avoiding metalorganic precursors. The size and morphology of the products were controlled successfully by adjusting the reaction conditions. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and X-ray photoelectron spectroscopy (XPS). The corresponding UV absorption and photoluminescence excitation spectra show a significant blue-shift confirming the quantum confinement effect. A possible growth mechanism for the formation of monodispersed Gd₂O₂S:Eu³⁺ nanocrystals has been proposed. The luminescence mechanism and the size dependence of their fluorescence properties are also discussed.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

Synthesis,photoluminescence and mechanoluminescence properties of Eu<Superscript>3+</Superscript> ions activated Ca<Subscript>2</Subscript>Gd<Subscript>2</Subscript>W<Subscript>3</Subscript>O<Subscript>14</Subscript> phosphors

A new series of Eu³⁺ ions-activated calcium gadolinium tungstate [Ca₂Gd₂W₃O₁₄] phosphors were synthesized by conventional solid-state reaction method. The X-ray diffraction patterns of the powder samples indicate that the Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors are of tetragonal structure. The prepared phosphors were well characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared spectroscopy (FTIR), photoluminescence (PL), and mechanoluminescence (ML) spectra. PL spectra of Eu³⁺: Ca₂Gd₂W₃O₁₄ powder phosphors have shown strong red emission at 615 nm (⁵D₀ → ⁷F₂) with an excitation wavelength λ _exci = 392 nm (⁷F₀ → ⁵L₆). The energy transfer from tungstate groups to europium ions has also reported. Mechanoluminescence studies of Eu³⁺: Ca₂Gd₂W₃O₁₄ phosphors have also been explained systematically.     

Synthesis and photoluminescence of Pb<Superscript>2+</Superscript> doped SrB<Subscript>2</Subscript>O<Subscript>4</Subscript>

Pure and Pb²⁺ doped SrB₂O₄ materials were prepared by a solution combustion synthesis method. The synthesized materials were characterized by using the powder XRD and FTIR. The photoluminescence properties of Pb²⁺ doped SrB₂O₄ materials were investigated using spectrofluorometer at room temperature. The emission and excitation bands of SrB₂O₄: Pb²⁺ was observed at 363 and 270 nm, respectively. The dependence of the emission intensity on the Pb²⁺ concentration for SrB₂O₄: Pb²⁺ was investigated and the critical Pb²⁺ concentration was determined The text was submitted by the authors in English.     

Color-tunable luminescence properties of Sm<Superscript>3+</Superscript>/Dy<Superscript>3+</Superscript> co-doped NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript> phosphors and their energy transfer mechanism

The Sm³⁺, Dy³⁺ doped and Sm³⁺/Dy³⁺ co-doped NaLa(MoO₄)₂ spherical phosphors were hydrothermally synthesized by the EDTA-2Na mediated method. Under the excitation of 297 nm, the quenching concentration of Sm³⁺ in NaLa(MoO₄)₂ host was determined to be 13%, and the concentration quenching mechanism was discussed to be the electric quadrupole–quadrupole interaction. After Sm³⁺ and Dy³⁺ ions were co-doped into the NaLa(MoO₄)₂ host, the energy transfer behaviors resulted from Dy³⁺ to Sm³⁺ ions were investigated by the help of the luminescent spectra of the obtained phosphors. By varying co-doping concentrations of Sm³⁺/Dy³⁺ ions, the emission color of NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ can be tuned from reddish-orange, pink and white to bluish-green. The CIE chromaticity coordinate, the correlated color temperature and the quantum efficiency of NaLa_0.87(MoO₄)₂:1%Sm³⁺, 12%Dy³⁺ were calculated to be (0.356, 0.320), 4353 K and 20%, respectively. Furthermore, in the temperature-dependent analysis, it presented good thermal stability, which can become a promising single-phased white-emitting phosphor for white LEDs devices. Based on these results, the possible energy transfer mechanism between Dy³⁺ and Sm³⁺ in NaLa(MoO₄)₂:Sm³⁺/Dy³⁺ was also proposed.     

Spectral parameters of Er<Superscript>3+</Superscript> ion in Yb<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>:KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystal

The spectral parameters of Er³⁺ in Yb³⁺/Er³⁺:KY(WO₄)₂ crystal with space group C2/c have been investigated based on Judd-Ofelt theory. The spectral parameters were obtained: the intensity parameters are: ₂ = 6.33 × 10^–20 cm², ₄ = 1.35 × 10^–20 cm², ₆ = 1.90 × 10^–20 cm². The radiative lifetime and the fluorescence branch ratios were calculated. The emission cross section _e (at 1536 nm) is 2.0 × 10^–21 cm².     

Persistent luminescence of Zn<Subscript>2</Subscript>GeO<Subscript>4</Subscript>:Mn<Superscript>2+</Superscript>/Pr<Superscript>3+</Superscript> phosphors

Zn₂GeO₄, Zn₂GeO₄:Mn²⁺, Zn₂GeO₄:Pr³⁺ and Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors were fabricated by a solid state reaction. The phase and luminescent properties of the fabricated phosphors were investigated. The XRD patterns show that all of the fabricated phosphors have an orthorhombic structure. The fabricated Zn₂GeO₄ shows an emission band in the range of 350–550 nm. The fabricated Zn₂GeO₄:Mn²⁺ and Zn₂GeO₄:Pr³⁺ phosphors show emission bands corresponding to Mn²⁺ and Pr³⁺ ions, respectively. The fabricated Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor shows the emission band results from Mn²⁺ and the codoped Pr³⁺ enhances the emission intensity of Mn²⁺. Moreover, Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphor exhibits longer decay time than that of Zn₂GeO₄:Mn²⁺. The higher intensity and longer lifetime of Mn²⁺ emission are induced by the energy transfer from Pr³⁺ of various vacancies to Mn²⁺ in Zn₂GeO₄:Mn²⁺/Pr³⁺ phosphors.     

X-ray diffraction,optical absorption and emission studies on Er<Superscript>3+</Superscript>- and Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>NbO<Subscript>4</Subscript> powder

Er³⁺(/Yb³⁺)-doped Li₃NbO₄ powder were prepared by thermally sintering mixtures of Er₂O₃ (0.5, 1.0 mol%), Yb₂O₃ (0, 0.5, 1.0 mol%), Li₂CO₃ (48–49 mol%) and Nb₂O₅ (50 mol%) at 1125, 1150 and 1450 °C over the durations of 8–22 h. The crystalline phases contained in these samples were determined by using X-ray diffraction and discussed in comparison with a vapor-transport-equilibration-treated (VTE-treated) Er(2.0 mol%):LiNbO₃ single crystal and ErNbO₄ powder previously reported. The results show that the X-ray patterns of the rare-earth-doped samples reveal little difference each other, but large differences with those of the VTE crystal and ErNbO₄ powder. The doped rare-earth ions Er³⁺ (and Yb³⁺) present in the powder as the ErNbO₄ (and YbNbO₄) phase(s). The possibility that the highly Er-doped LiNbO₃ crystal contains Li₃NbO₄ precipitates is small. Optical absorption and emission studies show that the only Er-doped Li₃NbO₄ powder shows similar absorption and emission characteristics with the pure ErNbO₄. The codopant Yb³⁺ ion enhances the 980-nm-upconversion emissions of Er³⁺ ions, results in remarkable spectral alterations at 0.98 μm region, and causes the alterations of relative absorbance and relative emission intensity of individual peaks or bands at 1.5 μm region. On the other hand, the Yb-codoping hardly affects the Er³⁺ energy structure and the lifetime of Er³⁺ ion at 1.5 μm. The measured lifetimes at 1.5 μm of Er³⁺ ions in the singly Er³⁺- and doubly Er³⁺/Yb³⁺-doped mixtures have a nearly same value of ∼ 1.5 ms. For the pure ErNbO₄ powder, the lifetime is prolonged to ∼2 ms perhaps due to radiation trapping effect.     

Structural and optical characterization of RE (Eu<Superscript>2+</Superscript>, Ce<Superscript>3+</Superscript>) doped SrMg<Subscript>2</Subscript>Al<Subscript>6</Subscript>Si<Subscript>9</Subscript>O<Subscript>30</Subscript> nanocrystalline phosphor

This article present the reports on optical study of Eu²⁺ and Ce³⁺ doped SrMg₂Al₆Si₉O₃₀ phosphors, which has been synthesized by combustion method at 550 °C. Here SrMg₂Al₆Si₉O₃₀:Eu²⁺ emission band observed at 425 nm by keeping the excitation wavelength constant at 342 nm, whereas SrMg₂Al₆Si₉O₃₀:Ce³⁺ ions shows the broad emission band at 383 nm, under 321 nm excitation wavelength, both the emission bands are assigned due to 5d–4f transition respectively. Further, phase purity, morphology and crystallite size are confirmed by XRD, SEM and TEM analysis. However, the TGA analysis is carried out to know the amount of weight lost during the thermal processing. The CIE coordinates of SrMg₂Al₆Si₉O₃₀:Eu²⁺ phosphor is observed at x?=?0.160, y?=?0.102 respectively, which may be used as a blue component for NUV-WLEDs. The critical distance of energy transfer between Ce³⁺ ions and host lattice is found to be 10.65 Å.     

Influence of Mg<Superscript>2+</Superscript>/Ga<Superscript>3+</Superscript> doping on luminescence of Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce<Superscript>3+</Superscript> phosphors

Mg²⁺/Ga³⁺ doped Y₃Al₅O₁₂:Ce³⁺ phosphors were synthesized through a solid state reaction. The phase and luminescent of the synthesized phosphors were investigated. For Ga³⁺ codoped Y_2.96Ce_0.04Al_(5?x)Ga_xO₁₂ phosphors, the emission intensity increases with the increase of Ga³⁺ concentration up to Y_2.96Ce_0.04Al_4.80Ga_0.20O₁₂ and then decreases with a further increase of Ga³⁺ concentration, but the emission peak shifts to shorter wavelength continuously in the Ga³⁺ doping concentration range of 0.05–0.25. For Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors, the emission intensity decreases and the emission peak shifts to longer wavelength continuously in the Mg²⁺ doping concentration range of 0.02–0.12. The emission spectra of Y_2.96Ce_0.04Al_(4.8?y)Ga_0.20Mg_yO₁₂ phosphors demonstrate that the codoped Mg²⁺/Ga³⁺ ions not only induce the enhancement of Y_2.96Ce_0.04Al₅O₁₂ emission intensity but also lead to the red shift of Y_2.96Ce_0.04Al₅O₁₂ emission peak. The decay lifetimes decrease in Mg²⁺/Ga³⁺ codoped Y_2.96Ce_0.04Al₅O₁₂ phosphors due to defects formed by substitutions of Y³⁺ by Mg²⁺/Ga³⁺.