An analysis of Y2O3:Eu thin films for thermographic phosphor applications

A comparative study of the luminescent properties of Y₂O₃:Eu³⁺ phosphor powders and thin films sputtered from targets prepared from combustion synthesized powders is reported. Thin films of (Y_0.96Eu_0.04)₂O₃ were deposited on silicon substrates. Films deposited at 600 °C had both monoclinic and cubic phases of Y₂O₃, which developed to an oriented cubic phase after annealing. Films and powders showed a linear dependence of the intensity of the ⁵D₇→⁷F₂ (611 nm) transition with temperature in the range 26-660 °C with an average rate of change of 1.8×10⁻⁴ °C⁻¹. The rate of change appears to be dependent on the Eu³⁺ concentration. This work shows that these thin films can be used as thermographic phosphors for remote temperature measurements.     

Fluorescence emission spectrum and energy transfer in Eu and Mn co-doped Ba2Ca(BO3)2 phosphors

Eu²⁺ and Mn²⁺ co-doped Ba₂Ca(BO₃)₂ phosphors yield two emission bands consisting of green and red components under the excitation of 360 nm, which shows a great potential for white LEDs. Effective energy transfer occurs in Eu²⁺/Mn²⁺ co-doped Ba₂Ca(BO₃)₂ host due to the large spectral overlap between the emission of Eu²⁺ and the excitation of Mn²⁺. The energy transfer from Eu²⁺ to Mn²⁺ is thoroughly investigated by their excitation, emission and photoluminescence decay behaviors, and is demonstrated to be via the dipole–quadrupole interaction.     

Ordered luminescent nanohybrid thin films of Eu(BA)3Phen nanoparticle in polystyrene matrix from diblock copolymer self-assembly

A simple route for fabricating highly ordered luminescent thin films based on hybrid material of diblock copolymer and europium complex, assisted with self-organization of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer upon solvent annealing, is presented. PS-b-PEO self-organized into hexagonal patterns and europium complex of Eu(BA)₃Phen was selectively embedded in PS blocks after solvent annealing in benzene or benzene/water vapor. During benzene annealing, the orientation of the PEO cylindrical domains strongly depended on the Eu(BA)₃Phen concentration. In contrast, when the hybrid thin films were annealed in mixture of benzene and water vapor, high degree of orientation of the PEO cylindrical domains is more easily obtained, which is independent of Eu(BA)₃Phen concentration. Furthermore, preferential interaction of PEO domains with water induces a generation of nanopores in the hybrid thin film. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to characterize the long-range lateral order and phase composition of the hybrid thin films. The ordered nanohybrid thin films kept the fluorescence property of Eu(BA)₃Phen and showed a strong red emission under the 254 nm light's irradiation. The fluorescence property was confirmed by photoluminescence (PL) spectra.     

Luminescence and energy transfer in Eu, Mn co-doped Li4SrCa(SiO4)2 for white light-emitting-diodes

Li₄(Sr_0.96Eu_0.04)(Ca_1 − xMn_x)(SiO₄)₂ phosphors were synthesized by solid-state reactions and photoluminescence (PL) properties were investigated. These phosphors have intense absorption in n-UV region, which is suitable for excitation of UV LEDs. The orange-reddish emission of Mn²⁺ can be adjusted by changing the Mn²⁺/Eu²⁺ ratio. Energy transfer from Eu²⁺ to Mn²⁺ is observed. Li₄(Sr_0.96Eu_0.04)(Ca_1 − xMn_x)(SiO₄)₂ phosphors could be used in white LEDs.     

Effect of Mg and Ti doping on the luminescence of Y2O3:Eu

The Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV materials (x_Eu: 0.02, x_Mg: 0.08, x_Ti: 0.04) were prepared by solid state reaction. The purity and crystal structure of the material was studied with the X-ray powder diffraction. Luminescence properties were studied in the UV-VUV range with the aid of synchrotron radiation. The emission of Y₂O₃:Eu³⁺,Mg²⁺,Ti^IV had a maximum at 612 nm (λ_exc: 250 nm) due to the ⁵D₀→⁷F₂ transition of Eu³⁺. The excitation spectra (λ_em: 612 nm) showed a broad band at 233 nm, due to the charge transfer transition between O²⁻ and Eu³⁺, and at 297 nm due to the Ti→Eu³⁺ energy transfer. Only very weak persistent luminescence was discovered. In the room and 10 K temperature excitation spectra, the line at 208 nm is due to the formation of a free exciton (FE) and a broad band at 199 nm was related to the valence-to-conduction band absorption of the Y₂O₃ host lattice. The absorption edge was ca. 205 nm giving 6.1 eV as the energy gap of Y₂O₃.     

Syntheses and electroluminescent properties of two europium ternary complexes Eu(DBM)3(PBO) and Eu(DBM)3(PBT)

Two europium complexes, Eu(DBM)₃(PBO) and Eu(DBM)₃(PBT) (DBM=dibenzoylmethanato, PBO=2-(2-pyridyl)benzoxazole, PBT=2-(2-pyridyl)benzothiazole), were prepared and used as emitting materials in organic electroluminescent (EL) devices. The devices with the structures ITO/TPD/Eu(DBM)₃(PBO) (or Eu(DBM)₃(PBT)/BCP/Alq₃/Mg:Ag/Ag emit red light originating from the europium complexes.     

Yb and Yb-Eu luminescent properties of the Li2Lu5O4(BO3)3 phase

The luminescence of Yb³⁺ in the oxyborate Li₂Lu₅O₄(BO₃)₃ is reported. At low temperature, in addition to the usual ytterbium infrared emission, this phosphor presents an emission in the ultraviolet () which corresponds to the transition from the charge transfer state (O-Yb) to the 4f levels of Yb³⁺. The temperature quenching Tq50% is equal to 120 K. The infrared emission studied at room temperature is located between 950 and 1100 nm.Europium emission quenching in the Li₂Yb₅O₄(BO₃)₃ phase is related to Eu→Yb transfer by cross-relaxation. The reverse Yb→Eu transfer by cooperative sensitization is highlighted in the codoped Li₂Lu₅O₄(BO₃)₃ compound.     

The luminescence properties of the ZnO@ZnWO4:Eu core–shell composites

The ZnO@ZnWO₄:Eu³⁺ core–shell composites were prepared by a two-step hydrothermal method and the photoluminescence properties of the composites were studied in contrast to the corresponding hexagonal ZnO and monoclinic ZnWO₄: Eu³⁺ nanocrystals prepared by the one-step hydrothermal method. The results demonstrate that in the nanocomposites the Eu³⁺ ions in the ZnWO₄ phase occupy two symmetry sites, one a well-crystalline inner site and one a disordered surface site; while in the ZnWO₄: Eu³⁺ nanocrystals, the local environments surrounding Eu³⁺ ions are relatively disordered for both the inner and the surface sites. This indicates that in the composites, the crystallinity of the ZnWO₄ becomes better, which have positive influence on the improvement of photoluminescence. The temperature stabilities for both the emissions of ZnO and Eu³⁺ ions are improved in contrast to the pure ZnO or ZnWO₄:Eu³⁺ nanocrystals.     

Photoluminescence studies on Eu and Ce-doped Li2SrSiO4

The luminescence of Li₂SrSiO₄: 0.01Eu, xCe (x=0.0025, 0.005, 0.0075, and 0.01) is studied as a potential ultraviolet light-emitting diode (UV-LED) phosphor that is capable of converting the ultraviolet emission of a UV-LED into white light with good luminosity. There are broad blue and yellow emissions peaked at 413 and 575 nm, respectively. The two emissions come from d-f transitions of Ce³⁺ and Eu²⁺, respectively. The emission intensity of Li₂SrSiO₄: 0.01Eu, xCe reaches its maximum at x=0.0075. The energy transfer from Ce³⁺ to Eu²⁺ is demonstrated to be the type of electric dipole-dipole interaction with considerable spectral overlap and nonradiative transition is calculated to dominate. The Commission International de I’Eclairage (CIE) chromaticity coordinates of Ce³⁺/Eu²⁺ substituted compounds is also discussed.     

Influence of Eu doping content on photoluminescence of Gd2O3:Eu phosphors prepared by liquid-phase reaction method

Europium-doped cubic Gd₂O₃:Eu³⁺ nanoparticles containing various activator content in the range of 5-15 wt% were synthesized by a liquid-phase reaction method to investigate the influence of Eu³⁺ loading on the optical properties of phosphors by using XRD, TEM, BET, spectrometer and fluorometer. The size of Gd₂O₃:Eu³⁺ powders was in the range 21-41 nm. The phosphors showed an initial increase in luminescence and then a subsequent decrease with further doping (above 10 wt%). The decay time was reduced with increasing Eu loading; however, it decreased significantly above the 10% Eu doping. From spectroscopic studies, the Eu³⁺ doping ion distribution was uniform and homogeneous up to the 10 wt% loading because no concentration quenching effect was observed. However, further Eu³⁺ doping above 10 wt% reduced the luminescence due to the concentration quenching effect, as deduced from the shortening of the decay time.     

Analysis on fluorescence of dual excitable Eu(TTA)3DPBT in toluene solution and PMMA

Photoluminescence of Eu(TTA)₃DPBT (TTA=thenoyltrifluoro-acetonate DPBT=2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) in toluene and PMMA thin film are measured with excitation at 350 and 404 nm, respectively, and analyzed using Judd-Ofelt theory. Under excitation at 350 nm, it is found that Eu(TTA)₃DPBT in toluene has a larger Ω₂ value (14.33×10⁻²⁰ cm²) than that (12.70×10⁻²⁰ cm²) of Eu(TTA)₃Phen (Phen=1,10-phenanthroline) in the same solvent, and has a smaller Ω₂ value (12.70×10⁻²⁰ cm²) in PMMA than that (Ω₂=14.09×10⁻²⁰ cm²) of Eu(TTA)₃Phen in PMMA. At the same time, it can be seen that under excitation at 350 nm Ω₂ value of Eu(TTA)₃DPBT in toluene is larger than that in PMMA. Excited by 404 nm, Ω₂ of Eu(TTA)₃DPBT obtained in toluene and in PMMA are the same as that excited at 350 nm. The transition probability (A), emission cross-section (σ) and the fluorescence branching ratio (β) are also evaluated. The lifetime of ⁵D₀ metastable state is measured on 350 and 404 nm excitation, respectively. For the former situation, it is 455 μs in toluene and 640 μs in PMMA, for the latter it is 460 μs in toluene and 664 μs in PMMA. By comparing absorptions with excitations, it can be found that DPBT is more efficient than TTA as an energy donor. Phosphorescence spectra are also measured to estimate the lowest triplet level and analyze the energy transfer for DPBT and TTA, from which it is found that the energy transfer from TTA to DPBT occurs in the luminescent process.     

Luminescence behavior of the Eu(TTFA)3 and TbSSA co-doped xerogel

Luminescence behavior of Eu(TTFA)₃ and TbSSA co-doped gel has been investigated. The excitation and emission spectra of the EuCl₃ and thenoyltrifluoroacetone co-doped gel appeared to exhibit intramolecular energy transfer from the coordinated thenoyltrifluoroacetonate to the europium ions, and the luminescence behavior of sulphosalicylic acid and TbCl₃ co-doped gel also indicated the synthesis of TbSSA in the gel. The luminescence behavior of x% Eu(TTFA)₃ and (1-x)% TbSSA (x=0-1) co-doped gel changed significantly with the ratio of Eu(TTFA)₃ and TbSSA. By adjusting the ratio of the Eu(TTFA)₃ and TbSSA in the gel, the luminescence of different colors which resulted from the mixture of the emission bands of Eu³⁺ ions and Tb³⁺ ions can be observed.     

Photoluminescence of double-color-emitting phosphor Ca5(PO4)3Cl:Eu, Mn for near-UV LED

Eu²⁺ activated Ca₅(PO₄)₃Cl blue-emitting phosphors were prepared by the conventional solid state method using CaCl₂ as the chlorine source and H₃BO₃ as flux. The structure and luminescent properties of phosphors depend on the concentrations of Eu²⁺, the amount of CaCl₂ and the usage of the H₃BO₃ flux were investigated systematically. Eu²⁺ and Mn²⁺ Co-doped Ca₅(PO₄)₃Cl with blue and orange double-band emissions were also researched based on the optimal composition and synthesis conditions. The energy transfer between Eu²⁺ and Mn²⁺ was found in the phosphor Ca₅(PO₄)₃Cl:Eu²⁺, Mn²⁺, and the Co-doped phosphor can be efficiently excited by near-UV light, indicating that the phoshor is a potentional candidate for n-UV LED used phosphor.     

Luminescence properties of novel NaBa4(BO3)3:Ce, Eu phosphors

Novel Eu³⁺, Ce³⁺ activated NaBa₄(BO₃)₃ phosphors were synthesized by solid-state reactions. The excitation spectrum of NaBa₄(BO₃)₃:Ce³⁺ consists of an intense band peaking at 350 nm and a weak band in the higher energy side, and the emission spectrum exhibits a blue band with a maximum at about 420 nm. The Eu³⁺ emission in NaBa₄(BO₃)₃ consists of the transitions from ⁵D₀ to ⁷F_J, and the excitation spectrum consists of broad excitation band peaking at 270 nm and some intense narrow lines. The optimum doped concentration, the critical distance of the concentration quenching, and the fluorescence lifetime have also been investigated.     

Enhanced luminescence from spontaneously ordered Gd2O3:Eu based nanostructures

Nanostructured Gd₂O₃:Eu³⁺ and Li⁺ doped Gd₂O₃:Eu³⁺ thin films were prepared by pulsed laser ablation technique. The effects of annealing and Li⁺ doping on the structural, morphological, optical and luminescent properties are discussed. X-ray diffraction and Micro-Raman investigations indicate a phase transformation from amorphous to nanocrystalline phase and an early crystallization was observed in Li⁺ doped Gd₂O₃:Eu³⁺ thin films on annealing. AFM images of Li⁺ doped Gd₂O₃:Eu³⁺ films annealed at different temperatures especially at 973 K show a spontaneous ordering of the nanocrystals distributed uniformly all over the surface, with a hillocks (or tips) like self-assembly of nanoparticles driven by thermodynamic and kinetic considerations. Enhanced photoemission from locations corresponding to the tips suggest their use in high resolution display devices. An investigation on the photoluminescence of Gd_2−xEu_xO₃ (x=0.10) and Gd_2−x−yEu_xLi_yO₃ (x=0.10, y=0.08) thin films annealed at 973 K reveals that the enhancement in luminescence intensity of about 3.04 times on Li⁺ doping is solely due to the increase in oxygen vacancies and the flux effect of Li⁺ ions. The observed decrease in the values of asymmetric ratio from the luminescence spectra of Li⁺ doped Gd₂O₃:Eu³⁺ films at high temperature region is discussed in terms of increased EuO bond length as a result of Li⁺ doping.     

Synthesis, luminescence and crystallographic structure of Eu-doped garnet-type yafsoanite Ca3Te2(ZnO4)3

A red-emitting phosphor of Eu³⁺-doped calcium–tellurium–zinc oxide, Ca₃Te₂(ZnO₄)₃, with a garnet-type structure was synthesized by high temperature solid-state reactions. This phosphor exhibited a strong red emission. The photoluminescence excitation spectrum showed that Ca₃Te₂(ZnO₄)₃:Eu³⁺ can be effectively excited by UV–visible light. The property of long-wavelength excitation for this material has a benefit as a red phosphor in application of white light-emitting diodes. The colour coordinates were calculated. The excitation and emission spectra and luminescence decay curves were obtained using a pulsed, tunable, narrowband dye laser. Crystallographic sites and charge compensation mechanism of Eu³⁺ ions were discussed. The emission line from Eu³⁺ in intrinsic crystallographic site in the lattice was located at 579.56 nm. The emission line from Eu³⁺ in another disturbed site, which is created by the defects created by the charge-compensation, was located at 580.88 nm. The disordered crystallographic sites of Eu³⁺ are benefit for their strong red luminescence corresponding to the ⁵D₀→⁷F₂ transition.     

Resonance induced divalent Eu states in EuF3 ultrathin layer

Resonant photoemission was used to investigate the EuF₃ ultrathin layer for the photon energies within the Eu 4d → 4f excitation region. Photoemission from the valence band in resonance showed the lines which can be attributed to two Eu valence states (Eu⁺³ and Eu⁺²) whereas the off resonance spectra of EuF₃ ultrathin layer do not exhibit divalent states of Eu. An explanation of that effect is proposed which is based on the charge transfer from the ligand.     

Eu/Tb ions co-doped white light luminescence Y2O3 phosphors

Y₂O₃:Eu³⁺, Tb³⁺ phosphors with white emission are prepared with different doping concentration of Eu³⁺ and Tb³⁺ ions and synthesizing temperatures from 750 to 950 °C by the co-precipitation method. The resulted phosphors were characterized by X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. The results of XRD indicate that the crystallinity of the synthesized samples increases with enhancing the firing temperature. The photoluminescence spectra indicate the Eu³⁺ and Tb³⁺ co-doped Y₂O₃ phosphors show five main emission peaks: three at 590, 611 and 629 nm originate from Eu³⁺ and two at 481 and 541 nm originate from Tb³⁺, under excitation of 250-320 nm irradition. The white light luminescence color could be changed by varying the excitation wavelength. Different concentrations of Eu³⁺ and Tb³⁺ ions were induced into the Y₂O₃ lattice and the energy transfer from Tb³⁺→Eu³⁺ ions in these phosphors was found. The Commission International de l’Eclairage (CIE) chromaticity shows that the Y₂O₃:Eu³⁺, Tb³⁺ phosphors can obtain an intense white emission.     

Terahertz spectroscopy of multiferroic EuFe3(BO3)4

The terahertz spectra of a rare-earth iron borate with the huntite structure are obtained for the first time. We study the low-temperature (4.0–90 K) α-polarized transmittance spectra of the EuFe₃(BO₃)₄ single crystal in the region 0.9–6.0 THz. Pronounced shifts of phonon frequencies and appearance of new phonon modes at the temperature _TS=58 K$T_S=58\text{K}$ of the R32→P₃₁21$R32\to P{3}_{1}21$ structural phase transition are observed. Additional shifts of phonon frequencies occur at the temperature _TN=34 K$T_N=34\text{K}$ of the magnetic ordering of the Fe subsystem, thus evidencing the spin–phonon coupling in this multiferroic material.     

Structural and luminescence characterization of synthetic Cr-doped Ni3(PO4)2

Ni_3–xCr_2x/3(PO₄)₂ (x=0 and 0.02) microcrystalline powders were obtained as single phases via a modified sol–gel Pechini-type in situ polymerizable complex method. The samples were characterized using scanning electron microscopy, X-ray diffraction, cathodoluminescence (CL), and thermoluminescence (TL) techniques. We found that Cr³⁺ doping modified the average particle and distribution. The mean particle size was 0.441 μm for Ni₃(PO₄)₂ and 0.267 μm for Ni_2.98Cr_0.013(PO₄)₂. The results also reveal that Cr³⁺ doping notably enhanced the CL and TL UV-blue emission.