Photoluminescence properties of NaGd(MoO4)2:Eu nanophosphors prepared by sol-gel method

NaGd(MoO₄)₂:Eu³⁺ (hereafter NGM:Eu) phosphors have been prepared by sol-gel method. The properties of the resulting phosphors are characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curve. The excitation spectra of NGM:Eu phosphors are mainly attributed to O → Mo charge-transfer (CT) band at about 282 nm and some sharp lines of Eu³⁺ f-f transitions in near-UV and visible regions with two strong peaks at 395 and 465 nm, respectively. Under the 395 and 465 nm excitation, intense red emission peaked at 616 nm corresponding to ⁵D₀ → ⁷F₂ transition of Eu³⁺ are observed for 35 at.% NGM:Eu phosphors as the optimal doping concentration. The luminescence properties suggest that NGM:Eu phosphor may be regarded as a potential red phosphor candidate for near-UV and blue light-emitting diodes (LEDs).     

Structure and luminescence properties of Eu/Tb codoped oxyfluoride glass ceramics containing Sr2GdF7 nanocrystals

Eu/Tb codoped transparent oxyfluoride borosilicate glass ceramics containing Sr₂GdF₇ nanocrystals were fabricated under a reductive atmosphere and the conversion of Eu³⁺ ions to Eu²⁺ ions was observed. The Sr₂GdF₇ nanocrystals with an average size of 32 nm were homogeneously precipitated in the oxyfluoride borosilicate glass matrix, which could be evidenced by X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray (EDX) spectroscopy. The enhancement of photoluminescence emission intensity, reduction of the relative emission intensities between ⁵D₀ → ⁷F₂ and ⁵D₀ → ⁷F₁, and long fluorescence lifetimes of Eu²⁺, Eu³⁺, and Tb³⁺ ions revealed that more rare earth ions were partitioned into the low phonon energy environment Sr₂GdF₇ nanocrystals. Under ultraviolet excitation, pure and bright white light emission was obtained in the oxyfluoride borosilicate glass ceramic, which may be a potential blue, green and red-emitting phosphor for white LEDs.     

Structure and scintillation of Eu-activated solid solutions in the BaBr2-BaI2 system

We report the structure and scintillation of Eu²⁺-activated solid solutions in the BaBr₂-BaI₂ system. Samples were synthesized in the form of ∼1 mm size crystals by melting the reactants in a sealed quartz tube followed by slow cooling. The solid solutions form an orthorhombic PbCl₂-type crystal structure with an ordered arrangement of the anions. Upon optical and X-ray excitation, the Eu²⁺-activated samples show an intense emission centered between 410 and 423 nm. The samples exhibit a fast decay characteristic of Eu²⁺, with the primary decay time between 315 and 600 ns for ∼75% of the total emitted light. Light yields for the compositions are compared to a newly discovered scintillator, BaBrI:Eu²⁺, measured under identical conditions.     

Synthesis and optical properties of KCaPO4:Eu phosphor

A series of Eu²⁺ doped KCaPO₄ phosphors were prepared by high temperature solid state reaction and an efficient blue-green emission was observed. The photoluminescence (PL) spectrum of the phosphor appeared one asymmetric peak under near-ultraviolet (n-UV) excitation and two emission bands at 480 nm and 540 nm were obtained using Gaussian fit, which was because Eu²⁺ ions inhabited two different Ca²⁺ sites: Eu(I) and Eu(II) in the host lattice, respectively. The excitation spectrum was a broadband extending from 250 to 450 nm, which matched well with the emission of ultraviolet light-emitting diodes (UV LEDs). The effect of Eu²⁺ concentration on the emission intensity of KCaPO₄:Eu²⁺ phosphor was investigated in detail.     

A red-emitting phosphor of fully concentrated Eu-based molybdenum borate Eu2MoB2O9

The fully concentrated Eu³⁺-based molybdenum borate Eu₂MoB₂O₉ was synthesized by the solid-state reaction method. The photoluminescence excitation and emission spectra, the temperature dependent luminescence intensities and the decay curve were investigated. Photoluminescence spectra show that the phosphor can be efficiently excited by near-UV light and exhibits an intense red luminescence corresponding to the electric dipole transition ⁵D₀ → ⁷F₂ at 615 nm. The luminescence intensities and color purity were investigated by increasing the fired temperatures. The phosphor shows the stable luminescence and color purity at high temperature.     

Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

Ag-catalyzed synthesis of europium borate Eu(BO2)3 nanowires, growth mechanism and luminescent properties

Eu(BO₂)₃ nanowires with diameters of 10-20 nm were fabricated through direct sintering Eu(NO₃)₃·6H₂O and H₃BO₃ with Ag as catalyst. The result of X-ray diffraction (XRD) indicated that the nanowire was single-crystalline with body-centered monoclinic structure. Based on the fact that Ag nanoparticles attached to the tips and middles of nanowires, a vapor-liquid-solid (VLS) growth mechanism of the Eu(BO₂)₃ nanowires is proposed. Three well-defined stages have been clearly identified during the process: Ag-Eu-B-O cluster process, crystal nucleation, and axial growth. The photoluminescence characteristics under UV excitation were investigated. The dominated Eu³⁺ orange-red emission corresponding to the magnetic dipole transition ⁵D₀ → ⁷F₁ is centered at 591 nm, indicating that Eu³⁺ is located at high symmetry crystal field with inversion center.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Luminescence properties of Eu ions in K2YF5 crystals

Luminescence properties of Eu³⁺ ions (0.1, 1.0 and 6.0 mol%) in K₂YF₅ crystals are investigated by the site-selective laser-excitation spectroscopy. The excitation spectrum of the ⁵D₀ emission exhibits two strong ⁷F₀ → ⁵D₀ excitation lines together with four weaker lines. Six different emission spectra are obtained under the excitation at each excitation line indicating that there existed at least six different sites for Eu³⁺. The relative intensity of the excitation lines is dependent on the Eu³⁺ concentrations. The ⁵D₀ emissions of Eu³⁺ show two types of decay behavior with lifetimes of 0.5 and 5.0 ms at 15 K. It is suggested that the fast and slow decays correspond to isolated and paired Eu³⁺ ions in K₂YF₅. The results are discussed in relation with one dimensional chain structure of the K₂YF₅ lattice.     

Hydrothermal synthesis, structure and scintillation characterization of nanocrystalline Eu-doped Gd2O3 materials and its X-ray imaging applications

Nanocrystalline Gd₂O₃:Eu scintillators were successfully synthesized using a hydrothermal method and subsequent calcination treatment in the electrical furnace as an X-ray to visible light conversion material for an indirect X-ray image sensor. In this work, various Gd₂O₃:Eu scintillators were prepared in accordance with different synthesis conditions such as doped-Eu concentration, different calcination temperatures of 600-1400 °C and calcination time of 1-10 h. The transition of morphology from nanorods to particles was observed as the calcination temperature of Gd₂O₃:Eu scintillator increased. And the phase transformation of the sample from cubic to monoclinic structure was discovered at 1300 °C calcination temperature. In addition, scintillation properties such as luminescent spectra and light intensity under 266 nm UV illumination were measured as a function of calcination condition of as-synthesized Gd₂O₃:Eu powder. The nanocrystalline Gd₂O₃:Eu scintillator with a strong red light emission at near 611 nm wavelength under photo- and X-ray excitation will be employed for its potential X-ray image sensor applications in the future.     

Novel red phosphors Na2CaSiO4:Eu for light-emitting diodes

Novel red phosphors Na₂CaSiO₄:xEu³⁺ were synthesized using high temperature solid-state reaction and their luminescence characteristics were investigated for the first time. The excitation spectra indicate that the Na₂CaSiO₄:xEu³⁺ phosphors can be effectively excited by ultraviolet (393 nm) light. The emission spectra of Na₂CaSiO₄:xEu³⁺ phosphors invariably exhibit four peaks assigned to the ⁵D₀-⁷F_J (J = 1, 2, 3 and 4) transitions of Eu³⁺ under 393 nm excitation. The Commission Internationale de l’Eclairage (CIE) chromaticity coordinates and quantum efficiency (QE) are (0.66, 0.34) and 58.9%, respectively. The good color saturation and high quantum efficiency indicate that Na₂CaSiO₄:Eu³⁺ phosphors are potential candidate for light-emitting diodes.     

A novel red phosphor NaLa4(SiO4)3F: Eu

A novel red phosphor NaLa₄(SiO₄)₃F: Eu³⁺ was synthesized by the conventional solid-state reaction at 950 °C for the first time. The luminescence properties of NaLa₄(SiO₄)₃F: Eu³⁺ were investigated, and the critical concentration of the activator concentration (Eu³⁺) was found to be 0.1 mol per formula unit. The phosphor presented red luminescence under the ultraviolet excitation of 254 or 395 nm, attributed to the transitions from ⁵D₀ excited states to ⁷F_J ( J = 0-4) ground states of Eu³⁺ ions. The results indicated that this newly-developed phosphor could find applications in tricolor fluorescent lamp, phosphor-liquid crystal displays and white lighting devices utilizing GaN-based excitation in the near UV.     

Uniform lanthanide-doped Y2O3 hollow microspheres: Controlled synthesis and luminescence properties

Lanthanide-doped uniform pure cubic phase Y₂O₃ hollow microspheres have been successfully synthesized via a facile, high yield urea-based coprecipitation route with assistant of carbon spheres templates. The diameter and shell thickness of the microspheres can be manipulated by adjusting carbon sphere templates. Under a 980 nm excitation, Yb³⁺/Er³⁺, Er³⁺, Yb³⁺/Tm³⁺-doped Y₂O₃ hollow microspheres emit bright upconversion red, green, blue light with high purity, respectively, while Eu³⁺, Eu³⁺/Tb³⁺-doped Y₂O₃ hollow microspheres exhibit intense downconversion red light under the excitation of 254 nm ultraviolet light. Especially, the 610 nm emission intensity of Eu³⁺ in the Eu³⁺/Tb³⁺-codoped Y₂O₃ hollow microspheres is almost 5 times of that in the Y₂O₃:Eu³⁺ hollow microspheres indicating the occurring of the energy transfer from Tb³⁺ to Eu³⁺ ions.     

Luminescent properties of Na3YSi3O9 doped with Eu under UV-VUV excitation

The luminescent properties of Na₃Y_1−xSi₃O₉:xEu³⁺ (0.05 ≦ x ≦ 0.80) powder crystals were investigated in UV-VUV region. The Eu³⁺-O²⁻ charge transfer band (CTB) was observed to be located at around 233 nm and the environmental parameter (h_e) was estimated to be about 0.730. The excitation spectrum monitoring the 613 nm red emission from Eu³⁺ ions reveals the host absorption band (HAB) to be around 145 nm. The calculated Commission Internationale de l’Eclairage (CIE) chromaticity coordinates indicate the emission by 233 nm rather than by 147 nm excitation has the better color purity and the possible mechanisms have been proposed. The Eu³⁺-emission showed high quenching concentration due to the isolated YO₆ octahedra in the host and the small h_e for the Eu³⁺ ions and the optimum concentration was determined to be as high as x = 0.65 and 0.30 with 233 and 147 nm excitation, respectively.     

A red phosphor for nUV LED based on (Y,Gd)BO3:Eu

(Y,Gd)BO₃:Eu³⁺ based phosphors were prepared by combustion technique followed by solid state sintering in air. The 4f-4f excitation at 394 nm of (Y_0.54Gd_0.46)_x (BO₃)_y:Eu³⁺ exhibits red emission at 593 nm. Its photoluminescence (PL) efficiency depends critically on the BO₃ to (Y,Gd) molar ratio. Optimal luminescence was obtained at the y/x molar ratio of 1.38. A 12-fold increase in its luminescence efficiency was seen with an increase in Eu concentration from 0.5 to 8.4 mol% at this y/x ratio. At 8.4 mol% of Eu concentration, the PL sensitivity of (Y_0.54Gd_0.46)_x (BO₃)_y:Eu³⁺ is 40% higher than that of the commercial (Y,Gd)BO₃:Eu³⁺ phosphor. In view of the high luminescence efficiency, this phosphor could serve as a potential candidate for application as a red phosphor for nUV LED apart from its known application in plasma display panels.     

Eu-doped LiF-SrF2 eutectic scintillators for neutron detection

Eu²⁺ 0.05%, 0.1%, and 0.2% activated LiF-SrF₂ eutectic scintillators were prepared by the Bridgman method using ⁶Li enriched (95%) raw material. The α-ray-induced radio luminescence spectra showed intense emission peak at 430 nm due to an emission from Eu²⁺ 5d-4f transition in the Eu:SrF₂ layers. When excited by ²⁵²Cf neutrons, all the samples exhibited almost the same light yields of 5000-7000 ph/n with a typical decay times of several hundreds ns.     

A luminescence spectroscopy study of scintillation crystals SrI2 doped with Eu

We report experimental study of luminescent properties of modern scintillation material SrI₂:Eu²⁺ carried out over the temperature range from 9 to 450 K by the means of the ultraviolet and vacuum ultraviolet spectroscopy with a time resolution. Photoluminescence of the Eu²⁺ ions at 2.85 eV was studied under both the intracenter and interband excitations, including an X-ray excitation. The bandgap of the SrI₂ crystal has been estimated on the basis of the obtained results. In the temperature range below 100 K the intrinsic luminescence at 3.4 eV was revealed and this emission band was assigned by its properties to the luminescence of self-trapped anionic excitons in SrI₂. The pronounced manifestation of the effect of multiplication of electronic excitations was revealed in the energy range above 2E_g.     

Energy transfer and luminescence properties of Eu-doped NaTb(WO4)2 phosphor prepared by a facile hydrothermal method

NaTb_(1−x)Eu_x(WO₄)₂ (x = 0-100%) phosphors have been synthesized via a mild hydrothermal process directly without further sintering treatment. X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence excitation and emission spectra and decay curve were used to characterize the samples. Moreover, the luminescence colors of NaTb_(1−x)Eu_x(WO₄)₂ (NTbW:Eu) samples can be tuned from green, green-yellow, and yellow to red by simply adjusting the relative Eu³⁺-doping concentrations under a single wavelength excitation, which might find potential applications in the light displays systems.     

Scintillation characteristics of Cs2LiCeBr6 crystal

This work investigates the scintillation properties of Cs₂LiCeBr₆ crystal as a new material for radiation detection. This scintillation material is grown by the vertical Bridgman method. Under X-ray excitation the sample crystal shows a broad cerium based emission band between 390 and 450 nm wavelength range. Energy resolution for 662 keV γ-rays is measured to be 7.4% (FWHM). At room temperature Cs₂LiCeBr₆ crystal exhibits three exponential decay time components. The fast and major component of scintillation time profile of Cs₂LiCeBr₆ emission decays with a 86 ns time constant. Absolute light yield for the sample crystal is estimated to be 27,000 and 29,000 photons/MeV using APD and photomultiplier tube, respectively. The sample crystal shows good proportionality of 5% in the measured energy range from 31 to 1333 keV. This study showed that this new scintillation crystal can be a good candidate for radiation detection and medical imaging. The sample crystal is highly hygroscopic.     

(Eu-Nb)-codoped TiO2 nanopowders synthesized via Ar/O2 radio frequency thermal plasma oxidation processing: Phase composition and photoluminescence properties through energy transfer

(Eu³⁺-Nb⁵⁺)-codoped TiO₂ nanopowders have been prepared by Ar/O₂ radio frequency (RF) thermal plasma oxidizing liquid precursor mists, with various addition contents of dopants (molar ratio of Eu³⁺:Nb⁵⁺ = 1:1). Characterizations have been performed by the combined studies of XRD, TEM, Raman spectra, UV-vis spectroscopy, and excitation and PL spectra. The plasma-generated nanopowders mainly consist of anatase and rutile polymorphs. Doping Nb⁵⁺ cannot have appreciable influence on Eu³⁺ solubility (0.5 at.%) in the TiO₂ host lattice, but can significantly inhibit the increase of rutile weight fraction for TiO₂. 617 nm PL intensity at 350 nm indirect excitation through energy transfer is considerably weaker than that at 467 nm direct excitation, indicating that a defect state level in the TiO₂ host lattice might be lowered below the excited state of Eu³⁺ by doping Nb⁵⁺, which is conceivable from a relatively large amount of oxygen deficiencies yielded in the TiO₂ host lattice.