Luminescent characterization of CaAl2S4:Eu powder

The photoluminescent (PL) emission and excitation behaviour of green-emitting CaAl₂S₄:Eu²⁺ powder phosphor is reported in detail. CaAl₂S₄:Eu²⁺ emission provides good CIE colour coordinates (x=0.141; y=0.721) for the green component in display applications. Powder with a dopant concentration of 8.5 mol% shows the highest luminescence efficiency. Temperature dependence of the radiative properties, such as luminescence intensity and decay time, was investigated. In particular, the Stokes shift, the mean phonon energy, the redshift, the energy of the f→d and d→f transition and the crystal field splitting of the CaAl₂S₄:Eu²⁺ emission were determined. The thermal quenching of the emission was examined.     

On photoluminescence in HgGa2S4

In this paper, we investigate the kinetics of photoluminescence in excited crystals of HgGa₂S₄ which have recently been proposed for implementing tunable luminescent devices. From photoluminescence experiments, performed at various temperatures and excitation powers, it appears that two kinds of radiative recombination processes take place during crystal excitation. These originate two bands in emission spectra which were resolved by means of a fitting procedure. The dependencies of these bands on temperature and excitation power density are explained by means of a specific kinetic model. A broad band, peaking at about 1.8 eV, is ascribed to electron-hole tunnel recombinations occurring in associated donor-acceptor pairs, according to a Prener-Williams scheme. The second narrow band, peaking at about 2.3 eV, is ascribed to electron-hole recombinations occurring in centres presenting short () and long-life () excited states. At room temperature, owing to thermally activated relaxation from short- to long-life states, these centres saturate under relatively low excitation powers. The tunability of photoluminescence is a consequence of competition between monomolecular and bimolecular recombination processes.     

Influence of co-doping different rare earth ions on CaGa2S4: Eu, RE(RE=Ln) phosphors

Photoluminescent phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE³⁺ including all rare earth ions except for Sc³⁺, Pm³⁺, Eu³⁺ and Lu³⁺) were prepared by sintering at high temperature in a reductive atmosphere, and their luminescent properties were studied intensively. The influences of co-doping rare earth ions on their luminescent properties were also investigated. No remarkable differences were found from excitation spectra of co-doped phosphors CaGa₂S₄: Eu²⁺, RE³⁺ in contrast with that of phosphor CaGa₂S₄: Eu²⁺, but there were a few differences in emission spectra of Ce³⁺, Pr³⁺ or Ho³⁺ co-doped phosphors. Phosphors CaGa₂S₄: Eu²⁺, RE³⁺ (RE=Ce, Pr, Gd, Tb, Ho and Y) had persistent afterglow, and very short afterglow was shown for Nd³⁺ or Er³⁺ co-doped phosphors, but no long afterglow appeared when auxiliary activator was La³⁺, Sm³⁺, Dy³⁺, Tm³⁺ or Yb³⁺. Among the phosphors with long-lasting phosphorescence, in our experiments, CaGa₂S₄: Eu²⁺, Ho³⁺ had the longest and the highest brightness long yellow afterglow. Thermo-luminescence of all co-doped phosphors was measured to find the answer of different influences from different rare earth auxiliary activators.     

Electronic structure of HgGa2S4

The electronic structure and chemical bonding in HgGa₂S₄ crystals grown by vapor transport method are investigated with X-ray photoemission spectroscopy. The valence band of HgGa₂S₄ is found to be formed by splitted S 3p and Hg 6s states at binding energies BE=3-7 eV and the components at BE=7-11 eV generated by the hybridization of S 3s and Ga 4s states with a strong contribution from the Hg 5d states. At higher binding energies the emission lines related to the Hg 4f, Ga 3p, S 2p, S 2s, Hg 4d, Ga LMM, Ga 3p and S LMM states are analyzed in the photoemission spectrum. The measured core level binding energies are compared with those of HgS, GaS, AgGaS₂ and SrGa₂S₄ compounds. The valence band spectrum proves to be independent on the technological conditions of crystal growth. In contrast to the valence band spectrum, the distribution of electron states in the bandgap of HgGa₂S₄ crystals is found to be strongly dependent upon the technological conditions of crystal growth as demonstrated by the photoluminescence analysis.     

Synthesis and luminescence properties of Tb:NaGd(WO4)2 novel green phosphors

Tb³⁺:NaGd(WO₄)₂ (Tb:NGW) phosphors with different Tb³⁺ concentrations have been synthesized by 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 Tb:NGW phosphors. XRD analysis confirmed the formation of NGW with scheelite structure. SEM study showed that the obtained Tb:NGW phosphors appeared to be nearly spherical and their sizes ranged from 1 to 1.5 μm. The excitation spectra of these systems showed an intense broad band with maximum at 270 nm related to the O→W ligand-to-metal charge-transfer state. Photoluminescence spectra indicated the phosphors emitted strong green light centered at 545 nm under UV light excitation. Analysis of the photoluminescence spectra with different Tb³⁺ concentrations revealed that the optimum dopant concentration for Tb³⁺ is about 15 at% of Tb³⁺ ions in Tb:NGW phosphors.     

Photoluminescence investigations of Zn2SiO4 co-doped with Eu and Tb ions

Zinc silicate phosphors co-doped with Eu³⁺ ions and also with both Eu³⁺ and Tb³⁺ ions were prepared by high temperature solid state reaction in air or reducing atmosphere. The luminescence characteristics of the prepared phosphors were investigated. While in the samples prepared in air, Eu³⁺ emission was found to be dominant over Tb³⁺ emission, in the samples prepared in reducing atmosphere, intense Eu²⁺ emission at 448 nm was found to be predominant over narrow Tb³⁺ emission. Luminescence studies showed that Eu³⁺ ions occupy asymmetric sites in Zn₂SiO₄ lattice. The intense f-f absorption peak of Eu³⁺ at 395 nm observed in these phosphors suggests their potential as red emitting phosphors for near ultra-violet light emitting diodes.     

Efficient VUV sensitization of Eu3+ emission by Tb3+ in potassium rare‐earth double phosphate

The luminescence properties of K₃Tb(PO₄)₂ activated by Eu³⁺ were studied at excitation over the 120–300 nm wavelength range. It is demonstrated that Tb³⁺ ions, exhibiting a strong absorption band in the vacuum‐ultraviolet (VUV), can provide efficient sensitisation of Eu³⁺ emission in this wave length range, giving rise to intense red luminescence at 150 nm excitation. A proof is given for the concept of VUV sensitisation enabling the engineering of luminescence materials with enhanced conversion efficiency of VUV radiation into visible light. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Low-temperature thermoluminescence in CaGa2S4:Eu

In the last years many insulating and semiconducting materials activated with rare-earth elements were found to exhibit phosphorescence and thermoluminescence properties, and are attracting increasing interest due to the variety of application of long-lasting phosphors. In this work we studied the phosphorescence decay and thermoluminescence properties of CaGa₂S₄:Eu²⁺ as a function of temperature in the 9-325 K range. The comparison between spectra recorded as a function of time delay from the excitation pulse at different temperatures indicates that long-lasting emissions peaked at about 2.2 eV occurs at Eu²⁺ sites. Thermoluminescence glow curve is characterized by five components at 69, 98, 145, 185 and 244 K. Experimental data are discussed in the framework of generalized order of kinetic model and allow to estimate the activation energies of trapping defects. The origin of glow components at 69, 98, 145 and 244 K is correlated to trapping defects induced by Eu²⁺ doping, while the component at 185 K is attributed to a continuous distribution of defects.     

Enhancement of red spectral emission intensity of Y3Al5O12:Ce phosphor via Pr co-doping and Tb substitution for the application to white LEDs

We have enhanced color-rendering property of a blue light emitting diode (LED) pumped white LED with yellow emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) phosphor using addition of Pr and Tb as a co-activator and host lattice element, respectively. Pr³⁺ addition to YAG:Ce phosphor resulted in sharp emission peak at about 610 nm through ¹D₂→³H₄ transition. And when Tb³⁺ substituted Y³⁺ sites, Ce³⁺ emission band shifted to a longer wavelength due to larger crystal field splitting. Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and (Y_1−xTb_x)₃Al₅O₁₂:Ce³⁺ phosphors were coated on blue LEDs to fabricate white LEDs, respectively, and their color-rendering indices (CRIs, R_a) were measured. As a consequence of the addition of Pr³⁺ or Tb³⁺, CRI of the white LEDs improved to be R_a=83 and 80, respectively. Especially, blue LED pumped (Y_0.2Tb_0.8)₃Al₅O₁₂:Ce³⁺ white LED showed both strong luminescence and high color-rendering property.     

Origin of green luminescence in PbWO4 crystals

Characteristics of two green emission bands, G(I) and G(II), and their origin were investigated within 0.4-300 K under photoexcitation in the 3.4-6.0 eV energy range for undoped and Mo⁶⁺-, Mo⁶⁺ , Y³⁺-, Mo⁶⁺, Nb⁵⁺-, Mo⁶⁺, Ce³⁺-, Cr⁶⁺-, La³⁺-, Ba²⁺- and Cd²⁺-doped PbWO₄ crystals with different concentrations of impurity and intrinsic defects, grown by different methods and annealed at different conditions. The G(I) emission band, observed at low temperatures, located around 2.3-2.4 eV and excited around 3.9 eV, is usually a superposition of many closely positioned bands. The G(I) emission of undoped crystals is assumed to arise from the WO₄²⁻ groups located in the crystal regions of lead-deficient structure. In Mo⁶⁺-doped crystals, this emission arises mainly from the MoO₄²⁻ groups themselves. The G(II) emission band located at 2.5 eV is observed only in the crystals, containing the isolated oxygen vacancies — WO₃ groups. This emission appears at T>160 K under excitation around 4.07 eV as a result of the photo-thermally stimulated disintegration of localized exciton states and subsequent recombination of the produced electron and hole centres near WO₃ groups. The G(II) emission accompanies also thermally stimulated recombination processes in PbWO₄ crystals above 150 K. Mainly the G(II) emission is responsible for the slow decay of the green luminescence in PbWO₄ crystals.     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

Red electroluminescent process excited by hot holes in SrGa2S4:Ce, Mn thin film

This paper reports the first observation of red electroluminescence (EL) in SrGa₂S₄:Ce, Mn thin film. The EL spectrum consists of single broad emission band having a peak wavelength of 665 nm. The dominant EL decay time was 31 μs. The relationship between the applied voltage and the EL waveform was measured in single insulating thin film electroluminescent (TFEL) devices. An asymmetric EL waveform was observed in SrGa₂S₄:Ce, Mn TFEL devices under a rectangular applied voltage. The polarity of the EL waveform in these devices was different from the waveform in manganese-activated zinc sulfide ZnS:Mn devices. This indicates that hot holes excite the Mn²⁺ ions to cause the red EL.     

Scintillation and anomalous emission in elpasolite Cs2LiLuCl6:Ce

The luminescence and scintillation properties of Cs₂LiLuCl₆:0.5%Ce³⁺ are presented. Special attention is devoted to a 9.4 ns fast emission at 275 nm that can only be excited via the highest cubic field 5d_e state of Ce. Contrary to Cs₃LuCl₆ and Cs₂LiYCl₆, where the same type of fast emission was observed, the emission in Cs₂LiLuCl₆ is still observed at room temperature. Assuming that the 5d_e state is located inside the host conduction band (CB), we propose that the emission originates from a mixed state at or just below the bottom of the CB and ends at the 4f ground state of Ce³⁺. To proof this model we studied the thermal quenching of the anomalous luminescence and performed X-ray photoelectron spectroscopy. A model for a temperature-activated energy transfer from the anomalous state to the lowest 5d_t excited state of Ce³⁺ explains most of the results. Besides the 275 nm emission, the material shows 5d_t-4f Ce³⁺ emission at 370 and 406 nm and 2 ns fast core-valence luminescence when excited with 16-22 eV photons. The scintillation properties of Cs₂LiLuCl₆:Ce are briefly discussed.     

Thermoluminescent properties of Eu and RE co-doped phosphors CaGa2S4:Eu, RE (RE=Ln, excluding Pm, Eu and Lu)

The thermo-luminescence (TL) of rare earth ions RE³⁺ (RE=Ln, excluding Pm, Eu and Lu) co-doped phosphors CaGa₂S₄:Eu²⁺, RE³⁺ was studied between room temperature and 300 °C, and 3D thermo-luminescence of the phosphors were measured from room temperature to 400 °C. The basic material CaGa₂S₄:Eu²⁺, showed at least two bands in the TL glow curve. Changing the auxiliary activator RE³⁺ (rare earth ion), intensities and the positions of the TL glow curve peaks were affected significantly. For the phosphors with long afterglow, auxiliary activator such as Ce³⁺, Pr³⁺, Gd³⁺, Tb³⁺, Ho³⁺, or Y³⁺ created some new defects in these compounds at lower trap levels and enhanced their TL intensities. The Nd³⁺ or Er³⁺ auxiliary activator only enhanced TL intensities to a low extent, so these two phosphors have short persistent luminescence at room temperature. TL intensities of La³⁺, Sm³⁺, Tm³⁺ or Yb³⁺ co-doped phosphors were suppressed greatly and no afterglow was shown. The relationship between auxiliary activators and corresponding thermo-luminescence curves of phosphors CaGa₂S₄:Eu²⁺, RE³⁺ are discussed in detail. According to our results, suitable activation energy and enough high corresponding trap density are necessary for the phosphor with long afterglow.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Eu substitution and particle size control of Y2O2S for the excitation by UV light emitting diodes

Yttrium oxysulfide doped with europium (Y₂O₂S:Eu³⁺) red phosphor is used in UV light emitting diodes (LEDs) by mixing with blue and green phosphors to generate white light which are important for the application in general lighting. Here, we demonstrate the effect of shape and size and the concentration of activator (Eu) of red Y₂O₂S phosphor.     

ESR spectra of Eu centers in defect Ga2S3 single crystals

In this paper, the author presents the results of measurements of the low-temperature and angular dependences of the ESR spectra of Eu²⁺ centers in defect Ga₂S₃ single crystals in the temperature range 8–29 K and for 0–180° orientations of the static magnetic field. The electron structure of impurity ¹⁵¹Eu atoms in Ga₂S₃:Eu single crystals has been studied by using the ESR method at different doping proportions of Eu atoms. Ga₂S₃ single crystals were grown from the melt using the Bridgman method. The Eu concentration was determined by atomic absorption analysis and X–ray fluorescence analysis (XRFA). By investigation on the ESR spectra, the author has first determined the values of charge states for Eu, which have turned out to be a Eu²⁺(4f⁷) ion with spin S=7/2, g=4.18±0.02 and concentration of the states of Eu N=6.3×10¹⁴ cm⁻³.     

Theoretical explanation of the g factor for Cr in Y2SiO5 crystal

The g factor of Cr⁴⁺ in Y₂SiO₅ crystal is calculated from a completed high-order perturbation formula, in which not only the conventional contribution to the g-shift Δg(=g−g_e) from the crystal-field mechanism, but also the contribution from the charge-transfer mechanism (which is neglected in the crystal-field theory) are considered. The calculated result shows good agreement with the observed value. It is found that the calculated Δg due to the charge-transfer mechanism is opposite in sign and about 38% in magnitude, compared with that due to the crystal-field mechanism. So, in the studies of the g factor for a 3dⁿ ion having high valence state in crystals, the contribution due to the charge-transfer mechanism should be taken into account.     

New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.