The Role of the Eu<Superscript>3+</Superscript> Concentration on the SrMoO<Subscript>4</Subscript>:Eu Phosphor Properties: Synthesis,Characterization and Photophysical Studies

SrMoO₄ doped with rare earth are still scarce nowadays and have attracted great attention due to their applications as scintillating materials in electro-optical like solid-state lasers and optical fibers, for instance. In this work Sr_1−xEu_xMoO₄ powders, where x = 0.01; 0.03 and 0.05, were synthesized by Complex Polymerization (CP) Method. The structural and optical properties of the SrMoO₄:Eu³⁺ were analyzed by powder X-ray diffraction patterns, Fourier Transform Infra-Red (FTIR), Raman Spectroscopy, and through Photoluminescent Measurements (PL). Only a crystalline scheelite-type phase was obtained when the powders were heat-treated at 800 °C for 2 h, 2θ = 27.8° (100% peak). The excitation spectra of the SrMoO₄:Eu³⁺ (λ_Em. = 614 nm) presented the characteristic band of the Eu^3 + 5L₆ transition at 394 nm and a broad band at around 288 nm ascribed to the charge-transfer from the O (2p) state to the Mo (4d) one in the SrMoO₄ matrix. The emission spectra of the SrMoO₄:Eu³⁺ powders (λ_Exc. = 394 and 288 nm) show the group of sharp emission bands among 523–554 nm and 578–699 nm, assigned to the ⁵D₁→⁷F_{0,1and 2} and ⁵D₀→⁷F_{0,1,2,3 and 4}, respectively. The band related to the ⁵D₀→⁷F₀ transition indicates the presence of Eu³⁺ site without inversion center. This hypothesis is strengthened by the fact that the band referent to the ⁵D₀→⁷F₂ transition is the most intense in the emission spectra.     

luminescence of BaGa<Subscript>2</Subscript>Se<Subscript>4</Subscript> crystals activated by Eu<Superscript>2+</Superscript> and Ce<Superscript>3+</Superscript> ions

We have studied the effect of doping with Eu²⁺ and Ce³⁺ ions on the photoluminescence (PL) of BaGa₂Se₄ crystals in the temperature range 77–300 K. We have established that the broad bands with maxima at wavelengths 456 nm and 506 nm observed in the photoluminescence spectra of BaGa₂Se₄:Ce³⁺ crystals are due to intracenter transitions 5d → ²F_7/2 and 5d →²F_5/2 of the Ce³⁺ ions, while the broad photoluminescence band with maximum at 521 nm in the spectrum of BaGa₂Se₄:Eu²⁺ is associated with 4f⁶ 5d → 4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ion. We show that in BaGa₂Se₄:Eu²⁺,Ce³⁺ crystals, excitation energy is transferred from the Ce³⁺ ions to the Eu²⁺ ions.     

Influence of magnetic ordering on electronic structure of Tb<Superscript>3+</Superscript> ion in TbFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal

Optical absorption spectra of trigonal crystal TbFe₃(BO₃)₄ have been studied in the region of ⁷F₆ → ⁵D₄ transition in Tb³⁺ ion depending on temperature (2–220 K) and on magnetic field (0–60 kOe). Splitting of the Tb³⁺ excited states, both under the influence of the external magnetic field and effective exchange field of the Fe-sublattice, have been determined. Landé factors of the excited states have been found. Stepwise splitting of one of the absorption lines has been discovered in the region of the Fe-sublattice magnetic ordering temperature. This is shown to be due to the abrupt change of equilibrium geometry of the local Tb³⁺ ion environment only in the excited state of the Tb³⁺ ion. In general, the magnetic ordering is accompanied by temperature variations of the Tb³⁺ local environment in the excited states. The crystal field splitting components have been identified. In particular, it has been shown that the ground state (in D ₃ symmetry approximation) consists of two close singlet states of A ₁ and A ₂ type, which are split and magnetized by effective exchange field of the Fe-sublattice. Orientations of magnetic moments of the excited electronic states relative to that of the ground state have been experimentally determined in the magnetically ordered state of the crystal. A pronounced shift of one of absorption lines has been observed in the vicinity of the TbFe₃(BO₃)₄ structural phase transition. The temperature interval of coexistence of the phases is about 3 K.     

Optical absorption spectra and magnetic phase transitions in TbFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Optical absorption spectra of the trigonal crystal of TbFe₃(BO₃)₄ in the vicinity of the ⁷F₆ → ⁵D₄ transition in a Tb³⁺ ion were studied as a function of temperature (2–70 K) and magnetic field strength (0–60 kOe) at 2 K. The splitting of the excited states of Tb³⁺ due to both the magnetic ordering of iron and an external magnetic field was determined. Abrupt splitting of the absorption lines of Tb³⁺ at temperature T_N of the magnetic ordering of the subsystem of iron was revealed, suggesting that the nature of such splitting is not entirely magnetic.     

Correlation of photoluminescence of (La,Ln) PO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript> (Ln = Gd and Y) phosphors with their crystal structures

Eu³⁺-doped (La, Ln) PO₄ (Ln = Gd and Y) phosphors were prepared by a facile co-precipitation method. Their structures and luminescent properties under UV excitation were investigated. Structural characterization of the nanostructured luminescence material was carried out with X-ray powder diffraction analysis. Scanning electron microscopy was carried out to understand the surface morphological features and grain sizes with 50–100 nm. It is found that (La, Gd) PO₄:Eu³⁺ phosphors have the same crystal structure as LaPO₄:Eu³⁺, which is monoclinic with a little different lattice parameters. In the case of (La, Y) PO₄:Eu³⁺ phosphors, however, the gradual change from monoclinic to tetragonal structure of host lattice was observed, as the amount of Y ion increased. From the photoluminescence spectra for (La, Ln) PO₄:Eu³⁺ (Ln = Gd and Y), the emission transition ⁵D₀ → ⁷F₁ has been found to be more prominent over the normal red emission transition ⁵D₀ → ⁷F₂. Furthermore, the size influence on the products was discussed. It was observed that the spectral features possess sharp and bright emission for potential applications on the monitors of the television and some other related electronic systems, in observing the images in orange–red color.     

Potential tunable white-emitting phosphor LiSr4(BO3)3:Ce3+, Eu2+ for ultraviolet light-emitting diodes

A novel Ce³⁺/Eu²⁺ co-activated LiSr₄(BO₃)₃ phosphor has been synthesized by traditional solid-state reaction. The samples could display varied color emission from blue towards white and ultimately to yellow under the excitation of ultraviolet (UV) light with the appropriate adjustment of the relative proportion of Ce³⁺/Eu²⁺. The resonance-type energy transfer mechanism from Ce³⁺ to Eu²⁺ in LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphors is dominant by electric dipole–dipole interaction, and the critical distance is calculated to be about 29.14 Å by the spectra overlap method. White light was observed from LiSr₄(BO₃)₃:mCe³⁺, nEu²⁺ phosphors with chromaticity coordinates (0.34, 0.30) upon 350 nm excitation. The LiSr₄(BO₃)₃:Ce³⁺, Eu²⁺ phosphor has potential applications as an UV radiation-converting phosphor for white light-emitting diodes.     

Study of frequency upconversion in Yb<Superscript>3+</Superscript>/Eu<Superscript>3+</Superscript> by cooperative energy transfer in oxyfluoroborate glass matrix

Oxyfluoroborate glass co-doped with Eu and Yb ions has been prepared and characterized for its optical properties through photoluminescence, absorption and lifetime measurements. An intense red upconversion is observed from the ⁵D₀ level of Eu³⁺ ions through energy transfer from Yb³⁺ to Eu³⁺ ion when excited with 980 nm. The Judd–Ofelt parameters have been evaluated to estimate the local site symmetry around the Eu³⁺ ions. These parameters have been used to derive radiative properties such as transition probabilities, branching ratios, radiative lifetimes and stimulated emission cross-sections for the ⁵D₀–⁷F_J transitions. Decay of excitation of the ⁵D₀ level has been measured by monitoring the ⁵D₀→⁷F₂ transition (613 nm) at room temperature. Quantum efficiency for this transition is found to be 73%. We also monitored the effect of temperature on the fluorescence emission of Eu³⁺. PACS 42.70.Ce; 42.70.Hj     

Luminescence characteristics of energy transfer between Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> in NaMgPO<Subscript>4</Subscript> phosphor

Powder samples of NaMgPO₄ doped with Eu²⁺ and Ce³⁺ were prepared and their photoluminescence spectra were systemically studied. Energy transfer from Ce³⁺ to Eu²⁺ in NaMgPO₄ phosphor was observed by investigating the optical properties from photoluminescence spectra in Eu²⁺ or Ce³⁺ singly doped and Eu²⁺–Ce³⁺ codoped sodium magnesium orthophosphates, NaMgPO₄. The enhancement of UV excitation is attributed to energy transfer from Ce³⁺ to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺–Eu²⁺ codoped NaMgPO₄ phosphors in which Eu²⁺ can be efficiently excited by 390 nm are potential candidates for phosphor-converted LEDs.     

Architectures of YF<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> solid and hollow sub-microspheres: a facile arginine-assisted hydrothermal synthesis and luminescence properties

Solid and hollow YF₃:Eu³⁺ spheres assembled by nanorods have been successfully synthesized via a facile arginine-assisted hydrothermal method and followed by a subsequent heat-treatment process. The experimental results reveal that the as-prepared YF₃:Eu³⁺ spheres are composed of the nanorods with a diameter of 20–50 nm and a length of 200–500 nm, the morphologies of YF₃:Eu³⁺ have been changed from solid to hollow spheres assembled by nanorods. With increase of hydrothermal temperature and time, the diameter of YF₃:Eu³⁺ spheres can be controlled from 300 to 800 nm. The solid and hollow spheres show an intense orange red emission peak near 595 nm, corresponding to the ⁵D₀ → ⁷F₁ transition of Eu³⁺. The possible formation mechanism for the hollow spheres has been presented in detail. This amine acid-assisted method is very simple, economic and environmental friendly for organic-free solvent, which would be potentially used in synthesizing other hollow materials.     

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)     

Sensitizer-dependent up-conversion of Ho<Superscript>3+</Superscript> in nanocrystalline Y<Subscript>2</Subscript>O<Subscript>3</Subscript>

Ho³⁺–Yb³⁺ co-doped Y₂O₃ nanocrystals were synthesized by firing hydroxy carbonate precursors. Yb³⁺-concentration-dependent up-conversion properties of Ho³⁺ in Y₂O₃ nanocrystals have been investigated. The relative intensity of up-converted red emission increases more quickly than that of the green and the near-infrared ones with the enhancement of the concentration of Yb³⁺. It is believed that the energy process ⁵ S ₂ (⁵F₄) (Ho) + ⁵ I ₇ (Ho) →⁵ I ₆ (Ho)+⁵ F ₅ (Ho) plays an important role in the population of the ⁵ F ₅ level of Ho³⁺. The result indicates that the intensity ratio of the green emission to the red one can be tuned by changing the sensitizer concentration. PACS 78.55.-m     

Ca₂BO₃Cl:Ce³⁺,Tb³⁺:A novel tunable emitting phosphor for white light-emitting diode

<正>Ca₂BO₃Cl:Ce³⁺,Ca₂BO₃Cl:Tb³⁺,and Ca₂BO₃Cl:Ce³⁺,Tb³⁺ phosphors are synthesized by a high temperature solid-state reaction.The emission intensity of Ce³⁺ or Tb³⁺ in Ca₂BO₃Cl is influenced by the Ce³⁺ or Tb³⁺ doping content,and the optimum concentrations of Ce³⁺ and Tb³⁺ are 0.03 mol and 0.05 mol,respectively.The concentration quenching effect of Ce³⁺ or Tb³⁺ in Ca₂BO₃Cl occurs,and the concentration quenching mechanism is d-d interaction for either Ce³⁺ or Tb³⁺.The Ca₂BO₃Cl:Ce³⁺,Tb³⁺ can produce colour emission from blue to green by properly tuning the relative ratio between Ce³⁺ and Tb³⁺,and the emission intensity of Tb³⁺ in Ca₂BO₃Cl can be enhanced by the energy transfer from Ce³⁺ to Tb³⁺.The results indicate that Ca₂BO₃Cl:Ce³⁺,Tb³⁺ may be a promising double emission phosphor for UV-based white light emitting diodes.     

Luminescence of Eu<Superscript>2+</Superscript> ions in alkaline earth dilithiosilicates

Spectral-luminescent properties of Eu²⁺ ions in alkaline earth dilithiosilicates of composition MLi₂SiO₄ (M = Ca, Sr, Ba) have been studied at 77 K. The reasons for the different positions of the Eu²⁺ 4f ⁶5 d → 4f ⁷ emission band maximum in spectra of MLi₂SiO₄ were found based on the obtained results. It was shown that the increase in the decay time of the Eu²⁺ emission on going from CaLi₂SiO₄ (0.41μs) through BaLi₂SiO₄ (0.64 μs) to Sr-silicate (1.11μs) correlates with the shift of the emission maximum to longer wavelengths.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

Rearrangement of optical centers and stimulated radiation of Eu<Superscript>3+</Superscript> in polycrystalline huntite under optical and electron-beam excitation

Polycrystalline europium huntite EuAl₃(BO₃)₄ has been prepared by solid-phase synthesis. The spectral and kinetic characteristics of its luminescence under the excitation by a xenon lamp, single laser pulse, and electron beam have been studied. It has been established that the laser excitation of the polycrystalline samples in the ⁷ F ₀ →⁵ L ₆ transition of Eu³⁺ ions with the power density P ≥ 5 × 10⁷ W/cm² leads to the structure rearrangement of the optical centers, which is accompanied by an increase in the probability of the radiation transitions of the activator. The stimulated radiation of the main type of Eu³⁺ centers in the ⁵ D ₀→⁷ F ₁, ⁷ F ₂, and ⁷ F ₄ transitions has been obtained under the excitation by the electron beam with an energy of 200 keV and a duration of 2 ns.     

Intense Upconversion Luminescence of Yb<Superscript>3+</Superscript>-Er<Superscript>3+</Superscript> in Li<Subscript>2</Subscript>O Content Tungsten-tellurite Glasses

The Er³⁺ -Yb³⁺ codoped in Li₂O content tungsten -tellurite (TWL) transparent glasses are synthesized and measured the absorption, Raman and upconversion luminescence (UPL) spectra. At room temperature intense green emission peak at 560 nm ( ⁴S_3/2→⁴I_15/2) and red emission peak at 670 nm ( ⁴F_9/2→⁴I_15/2) of Er³⁺ observed even at minimum 86 mW pumping power of infrared 980 nm excitation. For structure of the TWL glass, Raman spectrum result revealed that an important role of WO₃ in the formation of glass network linkage with Li₂O. Under this influence estimated lifetime of the ⁴I_11/2 of Er³⁺ was 1.89 μs and due to lower phonon energy of the glass produce strong upconversion signal. The effect of Er₂O₃ concentration on emission intensity result indicated that green emission intensity initially increase in compare to red emission. Under the 980 nm pump power variation measured the relatively increases the red emission to the green emission intensity and analyze the possible upconversion mechanism and process.     

Optical properties of pyridine funtionalized TbF<Subscript>3</Subscript> nanoparticles

The preparation of pyridine functionalized TbF₃ nanoparticles are described in this report. Synthesized nanoparticles were characterized using the TEM, UV/Vis, FTIR and photoluminescence spectroscopy. TEM micrograph reveals the nanorod shaped, uniform in size with a particles size in the range of 20–30 nm. FTIR spectrum shown characteristic absorption bands of pyridine and a small intensity band at 411 cm⁻¹ corresponding metal nitrogen ν(Tb–N) bonding. Uv-vis spectrum shown the characteristic absorption transitions of Tb³⁺ ion. A strong emission transition at 540 nm (⁵D₄ → ⁷F₅) was observed on excite by visible light at 414 nm.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Luminescence of transparent glass ceramics containing Er<Superscript>3+</Superscript> and Yb<Superscript>3+</Superscript> zirconate-titanate nanocrystals

Luminescence regularities have been studied in new erbium/ytterbium materials based on glasses and glass ceramics of a magnesium-aluminosilicate system containing nanoscale erbium/ytterbium zirconate titanate crystals with the pyrochlore structure. Lifetimes of Yb³⁺ and Er³⁺ ions in the ² F_5/2 state and in the ⁴I_11/2 and ⁴I_13/2 states, respectively, and the efficiency of Yb³⁺ → Er³⁺ energy transfer have been evaluated. The identified spectral-luminescent characteristics of the studied glasses and glass ceramics co-doped with erbium and ytterbium ions show that these materials are promising media for producing laser generation in the spectral range around 1.5 μm.     

Luminescence and energy transfer mechanism in Eu<Superscript>3+</Superscript>/Tb<Superscript>3+</Superscript>-co-doped ZrO<Subscript>2</Subscript> nanocrystal rods

Nanocrystal rods of Eu³⁺/Tb³⁺-co-doped ZrO₂ were synthesized using a simple chemical precipitation technique. Both ions were successfully doped into the Zr⁴⁺ ion site in a mixed structure containing both monoclinic and tetragonal phases. The Eu³⁺ or Tb³⁺ singly doped zirconia produced red and green luminescence which are characteristics of Eu³⁺ and Tb³⁺ ions, respectively. The co-doped zirconia samples produced blue emission from defect states transitions in the host ZrO₂, red and green luminescence from dopant ions giving cool to warm white light emissions. The phosphors were efficiently excited by ultraviolet and near-ultraviolet/blue radiations giving white and red light, respectively. The decay lifetime was found to increase with increasing donor ion concentration contrary to conventional observations reported by previous researchers. Weak quadrupole–quatdrupole multipolar process was responsible for energy transfer from Tb³⁺ (donor) ion to Eu³⁺ ion. No energy back-transfer from Eu³⁺ to Tb³⁺ ion was observed from the excitation spectra. Temperature-dependent photoluminescence shows the presence of defects at low temperature, but these defects vanished at room temperature and beyond. The Eu³⁺/Tb³⁺-co-doped ZrO₂ nanocrystal rod is a potential phosphor for white light application using UV as an excitation source. Thermoluminescence measurements show that the inclusion of Tb³⁺ ion increases trap depths in the host zirconia.