CaSc2O4:Eu: A tunable full-color emitting phosphor for white light emitting diodes

We report an intense full-color emission originating from ⁵D_0,1,2,3 to ⁷F_0,1,2,3,4 transitions of Eu³⁺ in CaSc₂O₄ upon 395 nm excitation. The emission spectra vary with increasing Eu³⁺ concentration, demonstrating tunable color coordinates from white to red region in the CIE chromaticity diagram. Considering the relaxation from ⁵D_J to ⁵D_J−1 through cross energy transfer, the Eu³⁺ concentration dependent emission spectra are well simulated based on the analysis of steady state rate equations and the measured lifetimes of the ⁵D_J levels. It is suggested that CaSc₂O₄:Eu³⁺ could be a potential single-phased full-color emitting phosphor for near-ultraviolet InGaN chip pumped white light emitting diodes.     

Synthesis and photoluminescence properties of new NaAlSiO4:Eu phosphors for near-UV white LED applications

A new NaAlSiO₄:0.1Eu²⁺ phosphors were synthesized at different temperatures using a liquid phase precursor (LPP) technique. The XRD patterns indicate the presence of hexagonal nepheline phase for all the samples. The synthesized phosphors can be excited efficiently in the broad near-UV region. The PL emission spectra showed a broad emission peak at around 551 nm corresponding to 5d → 4f transition of Eu²⁺ ions. The synthesized phosphors showed better thermal stability when compared with the standard YAG:Ce³⁺ phosphor.     

Synthesis and luminescent properties of SrAl2O4:Eu green-emitting phosphor for white LEDs

SrAl₂O₄:Eu²⁺ phosphor was prepared by a solid-state reaction in CO-reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of SrAl₂O₄:Eu²⁺. Field-emission scanning electron-microscopy (FE-SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 7–8 μm. Photoluminescence measurements showed that the phosphor can be efficiently excited by UV–visible light from 350 to 430 nm, and exhibited bright green emission peaked at about 516 nm. Bright green LEDs were fabricated by incorporating the phosphor with an InGaN-based UV chip. All the characteristics indicated that SrAl₂O₄:Eu²⁺ is a good candidate phosphor applied in white LEDs.     

EPR and vibrational studies of YVO4:Tm, Yb single crystal

A well oriented YVO₄ single crystal, with 5% Yb³⁺ and 2% Tm³⁺ nominal doping, was investigated using the Raman and EPR techniques.The EPR measurements suggest that Yb³⁺ ions occupy eight-coordinated Y³⁺ sites forming bisdisphenoids of the D_2d symmetry. An inhomogeneous distribution of rare-earth ions leads to a significant distortion of the local point symmetry (C₁). It seems that strong dipole–dipole interactions between Yb³⁺ ions are responsible for the distortion. As a result, two types of ytterbium magnetic centers appear. They correspond to paired magnetic centers and distorted isolated paramagnetic centers that are strongly sensitive to the magnetic field directions and some imperfections of the crystal. Pair centers can be recorded through the rotation around the c-crystal axis, whereas isolated centers can be measured when the crystal is rotated around the a-crystal axis. With the increasing temperature, the ytterbium signal disappeared at about 23 K and a group of narrow lines became visible. These lines, observed in the range of 240–550 mT, correspond to the Gd³⁺ (S = 7/2) ions, doped to the structure unintentionally from the basic materials.     

Synthesis of monodisperse spherical core-shell SiO2-SrAl2Si2O8: Eu2+ phosphors by hydrothermal homogeneous precipitation method

Abstract

Nanocrystalline SrAl₂Si₂O₈ :Eu²⁺ phosphor layers were coated on nonaggregated, monodisperse and spherical SiO₂ particles using a hydrothermal homogeneous precipitation. After annealing at 1100 °C, core-shell SiO₂@SrAl₂Si₂O₈ :Eu²⁺ particles were obtained. They were characterized with x-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. XRD analysis confirmed the formation of SiO₂ @SrAl₂Si₂O₈ :Eu²⁺ particles; it indicated that the SrAl₂Si₂O₈ :Eu²⁺ shells on SiO₂ particles consisted of hexagonal crystallites. The core-shell phosphors obtained are well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the coated layer is approximately 20–40 nm. Under ultraviolet excitation (361 nm), the particles emit blue light at about 440 nm due to the Eu²⁺ ions in their shells.     

Synthesis of monodisperse spherical core-shell SiO2-SrAl2Si2O8: Eu2+ phosphors by hydrothermal homogeneous precipitation method

Nanocrystalline SrAl₂Si₂O₈ :Eu²⁺ phosphor layers were coated on nonaggregated, monodisperse and spherical SiO₂ particles using a hydrothermal homogeneous precipitation. After annealing at 1100 °C, core-shell SiO₂@SrAl₂Si₂O₈ :Eu²⁺ particles were obtained. They were characterized with x-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy and photoluminescence techniques. XRD analysis confirmed the formation of SiO₂ @SrAl₂Si₂O₈ :Eu²⁺ particles; it indicated that the SrAl₂Si₂O₈ :Eu²⁺ shells on SiO₂ particles consisted of hexagonal crystallites. The core-shell phosphors obtained are well-dispersed submicron spherical particles with a narrow size distribution. The thickness of the coated layer is approximately 20–40 nm. Under ultraviolet excitation (361 nm), the particles emit blue light at about 440 nm due to the Eu²⁺ ions in their shells.     

Low-temperature synthesis of Y2SiO5:Eu powders using mesoporous silica and their luminescence properties

This paper reports the synthesis of Eu³⁺ ions-doped Y₂SiO₅ (Y₂SiO₅:Eu³⁺) powders by mesoporous template route. Using mesoporous silica SBA-15 as silica source, Y₂SiO₅:Eu³⁺ powders were prepared by solid-state reaction at a calcination temperature of 1300 °C without fluxes. The prepared Y₂SiO₅:Eu³⁺ powders were characterized by X-ray diffraction, scanning electron microscope, nitrogen adsorption-desorption isotherms, and photoluminescence spectroscopy. The results show that the crystalline Y₂SiO₅:Eu³⁺ particles are dense and have a morphology similar to SBA-15. The low calcination temperature is attributed to the high reactive activity of SBA-15 with large surface area and non-crystalline structure. The Y₂SiO₅:Eu³⁺ powders prepared at a low calcination temperature show luminescence properties similar to the reported results of Eu³⁺ doped-Y₂SiO₅ samples prepared at high temperatures.     

Dynamical processes of energy transfer in red emitting phosphor CaMoO4:Sm, Eu

Upon ⁴K_11/2 excitation of Sm³⁺ at 405 nm, the performance of energy transfer from Sm³⁺ to Eu³⁺ in the red emitting phosphor CaMoO₄:Eu³⁺, Sm³⁺ significantly extends its excitation region for better matching the near-UV LED. Photoluminescence spectra indicate that the energy transfer pathway concerns the relaxation from ⁴K_11/2 to ⁴G_5/2 of Sm³⁺ and subsequent transfer to ⁵D₀ of Eu³⁺ rather than ⁵D₁ of Eu³⁺. The fluorescent decay pattern of Sm³⁺⁴G_5/2 level in CaMoO₄:0.5% Sm³⁺, 2% Eu³⁺ is studied at 77 K based on the Inokuti-Hirayama formula, revealing an electronic dipole-dipole interaction between Sm³⁺ and Eu³⁺. The coefficient for the energy transfer is obtained to be 8.5 × 10⁻⁴⁰ s⁻¹ cm⁶. The fluorescence rise and decay pattern of Eu³⁺⁵D₀ level as Sm³⁺ is only excited at 77 K is well described by the dynamical processes of the energy transfer.     

Synthesis and luminescent properties of LaPO4:Eu microspheres

LaPO₄:Eu³⁺ microspheres were synthesized, using LaCl₃, EuCl₃ and (NH₄)₂HPO₄ as starting materials. The morphology, formation mechanism, and luminescent property of samples were systemically studied. X-ray diffraction (XRD) and infrared spectroscopy (IR) show that LaPO₄:Eu³⁺ microspheres have a pure monoclinic phase. Cetyltrimethyl ammonium bromide (CTAB) usually forms spherical micelles above a critical micelle concentration, which plays an important role in the formation of LaPO₄:Eu³⁺ microspheres. The excitation spectrum of LaPO₄:Eu³⁺ microspheres consists of several sharp lines due to the direct excitation of the Eu³⁺ cations from the ground state to higher levels of the 4f-manifold. The emission intensity of microspheres is higher than irregular particles because of the lowlier surface area. The lifetimes of Eu³⁺ ions in the LaPO₄:Eu³⁺ microspheres are determined to be 2.41 ms.     

Self-assembled 3D flower-like NaY(MoO4)2:Eu microarchitectures: Hydrothermal synthesis, formation mechanism and luminescence properties

Self-assembled 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were successfully synthesized by a glycine-assisted hydrothermal method at 180 °C. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing the time of hydrothermal reaction system. 3D flower-like NaY(MoO₄)₂:Eu³⁺ microarchitectures were formed with 72 h reaction time. The formation mechanism for flower-like architecture was proposed on the basis of a series of time-dependent experiments. The NaY(MoO₄)₂:Eu³⁺ powders obtained can be effectively excited by 396 nm light, and exhibit strong red emission around 615 nm, attributed to the Eu³⁺⁵D₀ → ⁷F₂ transition. An investigation on the photoluminescence (PL) properties of NaY(MoO₄)₂:Eu³⁺ obtained revealed that the luminescence properties were correlated with the morphology and size.     

Preparation of SrAl2O4: Eu, Dy nanometer phosphors by detonation method

SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer phosphors were synthesized by detonation method. The particle morphology and optical properties of detonation soot that was heated at different temperatures (600–1100 °C) had been studied systematically by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results indicated SrAl₂O₄: Eu²⁺, Dy³⁺ nanometer powders in monoclinic system (a = 8.442, b = 8.822, c = 5.160, β = 93.415) can be synthesized by detonation method, when detonation soot was heated at 600–800 °C. The particle size of SrAl₂O₄: Eu²⁺, Dy³⁺ is 35 ± 15 nm. Compared with the solid-state reaction and sol-gel method, synthesis temperature of the detonation method is lower about 500 and 200 °C respectively. After being excited under UN lights, detonation soot and that heated at 600–1100 °C can emit a green light.     

Radioluminescence and photoluminescence of hafnia-based Eu-doped phosphors

Crystal structures of hafnia are discussed and it is shown that addition of about 7 at.% of Lu to the HfO₂ host lattice enforces the mixed composition to crystallize in cubic structure even at room temperature. Without Lu HfO₂ crystallizes in monoclinic structure. Luminescence and luminescence excitation spectra of Hf_0.93Lu_0.07O_1.965 are presented and discussed for powders prepared at different temperatures (600–1000 °C) and with different content of Eu. It is shown that decay of the 595.4 nm luminescence is longer (2.5 ms) than the 610 nm (1.6 ms). Radioluminescence efficiency of the cubic Hf_0.93Lu_0.07O_1.965 is low and does not exceed 10% of the commercial Gd₂O₂S:Eu.     

Luminescent properties of Eu doped α-Gd2(MoO4)3 phosphor for white light emitting diodes

A novel red emitting phosphor α-Gd₂(MoO₄)₃:Eu³⁺ was developed for white light emitting diodes (LEDs). The phosphor was prepared by solid-state reaction. The effects of the flux content and the activator concentration on the crystal structure, morphology and luminescent properties were investigated by using XRD, SEM, and fluorescent spectra. These results showed that this phosphor can be effectively excited by ultraviolet (UV) (395 nm) and blue (465 nm) light, matching the output wavelengths of ultraviolet or blue LED chips. The α-Gd₂ (MoO₄)₃ phosphor may be a better candidate for solid state lighting application.     

Effects of Zn doping on the structural and luminescent properties of Sr4Si3O8Cl4:Eu phosphors

Sr₄Si₃O₈Cl₄: Eu²⁺ phosphors were synthesized by the solid-reaction at high temperature. The emission intensity reaches a maximum at 0.08 mol% of Eu²⁺ concentration. The present paper mainly focused on the effects of Zn²⁺ on the crystallization behavior and photoluminescence (PL) properties of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. Results suggested that no new phase is introduced by co-doping with a small amount of Zn²⁺ ions, but when co-doped with excessive amount of Zn²⁺ ions, Sr₂ZnSi₂O₇ appears. We find that the co-doping of a small amount of Zn²⁺ could remarkably improve the PL intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺. When x = 0.05, the intensity of Sr₄Si₃O₈Cl₄:0.08Eu²⁺,xZn²⁺ was increased up to 2.3 times that of pure Sr₄Si₃O₈Cl₄:0.08Eu²⁺, which could be attributed to the flux effect of Zn²⁺ ions, and the Zn²⁺ doping reduces the opportunities of the energy transfer between Eu²⁺.     

Luminescent properties of Ca2BO3Cl:Eu yellow-emitting phosphor for white light-emitting diodes

The Ca₂BO₃Cl:Eu²⁺ phosphor was synthesized by the general high temperature solid-state reaction and an efficient yellow emission under near-ultraviolet and blue excitation was observed. The emission spectrum shows a single intense broad emission band centered at 573 nm, which corresponds to the allowed f-d transition of Eu²⁺. The excitation spectrum is very broad extending from 350 to 500 nm, which is coupled well with the emission of UV LED (350-410 nm) and blue LED (450-470 nm). The measured emission of In-GaN-based Ca₂BO₃Cl:Eu²⁺ LED shows white light to the naked eye with a chromatic coordinate of (0.33, 0.36). The Ca₂BO₃Cl:Eu²⁺ is a very appropriate yellow-emitting phosphor for white LEDs.     

Yellow-emitting phosphor of Sr3B2O6:Eu for application to white light-emitting diodes

This work focuses on the development of Eu²⁺-doped strontium (Sr)-borate as a yellow-emitting phosphor and its application to the fabrication of white light-emitting diodes (LEDs). Synthesis of Eu²⁺-doped Sr-borate phosphors was finely tuned for obtaining the efficient yellow luminescence through varying host composition, Eu concentration, and firing temperature. The 1300 °C-fired Eu²⁺-doped Sr₃B₂O₆, which was found to be the most efficient candidate to date, was used for white LED fabrication. Their optical properties were evaluated, resulting in warm white lights with CIE chromaticity coordinates of (0.340–0.372, 0.287–0.314) and color rendering indices of 75–77 under the forward currents of 5–40 mA.     

YAG:Ce3+, Gd3+ nano-phosphor for white light emitting diodes

YAG:Ce³⁺, Gd³⁺ nano-phosphors were synthesised by the glycothermal method. The X-ray diffraction measurements showed that the samples can be well-crystallised at 600°C. The transition electron microscope showed that the particles have sizes mostly in the range between 35 and 100?nm. The YAG:Ce nano-phosphor had a wide emission band ranging from blue to yellow with a peak at 532?nm, due to the transition from the lowest 5d band to ²F_7/2, ²F_5/2 states of the Ce³⁺ ion. Red-shift of emission peak wavelength from 532 to 568?nm was achieved doping Gd³⁺ ions into the YAG:Ce³⁺ to substitute some Y³⁺ ions. White light emitting diodes (LEDs) were obtained by combining blue LED chip (InGaN-based 460?nm emitting) with (Y_{2.94? x} Ce_0.06Gd _x )Al₅O₁₂ phosphor. As x has the value of 0.8, an intense white LED with good colour rendering of 86 was obtained.     

Low temperature luminescence of KMgF3:Eu crystal

Paper presents luminescence spectra and time resolved spectra of KMgF₃:Eu²⁺ system obtained at different temperatures and pressures, under excitation with 325 nm. At temperatures between 200 K and 292 K the spectra consist of sharp line peaked at 27,830 cm⁻¹ related to ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺ accompanied by the phonon sideband. Under pressure the red spectral shift with the rate equal to −0.6 cm⁻¹/kbar is observed. Luminescence decay is single-exponential with the lifetime equal to 5.2 ms independent of pressure and temperature. The emission spectra obtained at temperatures lower than 125 K consist of 5 sharp lines peaked at 27,590 cm⁻¹, and 27,670 cm⁻¹, 27,722 cm⁻¹, 27,766 cm⁻¹ and 27,809 cm⁻¹, that relative intensity depends on temperature. Pressure shift of these lines was found to be equal to −0.6 cm⁻¹/kbar; the same as ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺, whereas their lifetime is shorter and is equal to 0.7 ms at 100 K. These new lines disappear at temperature greater than 200 K. We tentatively related them to the luminescence of Eu²⁺-F center (fluorine vacancy with electron) complex.     

Enhanced red emission in ZnB2O4:Eu by charge compensation

Eu³⁺ doped ZnB₂O₄ without or with different charge compensation (CC) approaches (co-doping Li⁺, Na⁺, K, decreasing the content of Zn²⁺) were prepared by solid state reactions. The phosphors can strongly absorb 393 nm ultraviolet (UV) light which is coupled well with the emission of currently used InGaN-based near UV light emitting diodes (LEDs) and emit red light with a good color purity. The luminescent intensity of phosphors can be remarkably enhanced with any of CC methods. However, the shape and position of excitation and emission spectra keep unchanged. The introduction of Li⁺ can enhance the red emission intensity of Eu³⁺ by ∼4 times with the optimal effect. Red emission of Eu³⁺ can also be enhanced with the other three CC approaches but the effects are not as good as Li⁺ because the volume unbalance in Li⁺ compensation approach is the smallest while net positive charge was offset. The results of this work suggest that volume compensation and equilibrium of mole number should also be taken into account when a CC approaches is selected.