A potential Eu-activated Ca10K(PO4)7 red phosphor for white light-emitting diodes

New red Ca₁₀K(PO₄)₇:Eu³⁺, K⁺ phosphors were synthesized by solid state reaction and their photoluminescence properties as well as those by co-doping Mo⁶⁺ under near ultraviolet excitation were investigated. From the excitation spectra monitored at 611 nm, it can be seen that the strongest excitation peak is situated at 393 nm, well matching with the emission wavelength of near-ultraviolet chips for white LEDs. Upon 393 nm excitation, the brightness of Ca₉K(PO₄)₇:0.5Eu³⁺, 0.5 K⁺ with the optimal Eu³⁺-doping concentration is about 2.3 times stronger than that of the commercial red Y₂O₃:Eu³⁺ phosphor. The introducing of Mo⁶⁺, which results in a possible variety for the excited energy level of the host, can enhance the brightness of Eu³⁺ to be maximized by about 15%. The CIE chromaticity coordinates of Ca₉K(PO₄)₇:0.5Eu³⁺, 0.5 K⁺ are calculated to (0.654, 0.345), which are close to the (0.67, 0.33) standard of the National Television System Committee. All the above results indicate Eu³⁺-activated Ca₁₀K(PO₄)₇ is a potential candidate for white LEDs.     

Solid state-hydrothermal synthesis and photoluminescence of LaVO4: Eu nanophosphors

A modified hydrothermal process is engaged in the synthesis of LaVO₄: Eu³⁺ nanophosphor. All kinds of inorganic salts (solid state hydrated rare earth nitrates and NH₄VO₃) and precipitation reagents (ammonia and urea) are mixed to form the solid state precursors instead of general aqueous solution systems, and a little amount water exists in the hydrothermal reaction systems. Both X-ray powder diffraction (XRD) and transmission scanning electronic microscope (TEM) shows that the uniform microstructure with the particle size of around 60 nm and the product from ammonia possesses the higher phase purity than that from urea. LaVO₄: Eu³⁺ shows a strong red emission at 617 nm originating from the ⁵D₀ → ⁷F₂ hypersensitive transition of Eu³⁺ ion. Especially the LaVO₄: Eu³⁺ nanophosphor from ammonia presents the more excellent photoluminescent property (lifetime and quantum efficiency) than that from urea.     

Photoluminescence properties of Eu doped Ba2ZnS3 phosphor for white light emitting diodes

The synthesis and photoluminescence properties of novel Eu²⁺ doped Ba₂ZnS₃ phosphors for white light emitting diodes (LEDs) are reported. Diffuse reflection spectra of Ba₂ZnS₃ host and synthesized phosphors have been measured. The excitation spectra of synthesized phosphors consist of three broad bands between 250 nm and 550 nm and are consistent with the diffuse reflectance spectra. The emission spectra show the characteristic 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ion and there exists efficient energy transfer from host to Eu²⁺ ions when excited by 350-nm light. The dependence of emission spectra on temperature is also measured; the possible reasons applied to explain the experimental results are also discussed. The fluorescence lifetime of Eu²⁺ in Ba_1.995ZnS₃:0.005Eu²⁺ is measured and the values are 1.49 and 23.4 μs.     

Enhanced luminescence by charge compensation in red-emitting Eu-activated Ca3Sr3(VO4)4

The effects of charge compensation on the luminescence behavior of a red-emitting phosphor, Ca₃Sr₃(VO₄)₄:Eu³⁺, were investigated. It has been observed that charge compensated by monovalent ions, especially Na⁺, shows greatly enhanced red emission under ultraviolet excitation. It is found that Na₂CO₃ addition acts as a fluxing agent and plays a role in charge compensation, which clearly improves the emission intensity of Eu³⁺-activated Ca₃Sr₃(VO₄)₄. Enhanced emission intensity of the corresponding charge compensated phosphors under ultraviolet radiation may find application in the production of red phosphors for white light-emitting diodes.     

Spectroscopic properties of Eu-doped KLa(PO3)4 and LiLa(PO3)4 powders

KLa(PO₃)₄ (KLP) and LiLa(PO₃)₄ (LLP) doped with different concentrations of Eu³⁺ are grown by solid state reaction. The obtained powders are identified by X-ray diffraction, Raman and FT-IR spectroscopies. These polyphosphates KLa(PO₃)₄ and LiLa(PO₃)₄ crystallize in the monoclinic system but with different space groups respectively P2₁ and C2/c. The evolution of crystal lattice parameters as function of Eu³⁺ concentration in these host lattices was studied. Spectroscopic properties of the Eu³⁺-doped KLa(PO₃)₄ and LiLa(PO₃)₄ at room temperature (RT) are presented. The excitation spectra of the Eu³⁺ ion in condensed polyphosphates along the UV-Visible domain are registered. They show that the position of the charge transfer band (CTB) depends on the host lattices. The effect of structural characteristics of condensed polyphosphates on their optical and colorimetric properties was investigated for the first time. Colorimetric parameters of the Eu³⁺ ions red emission in KLP and LLP are determined and compared with other host matrices. Evolution of colorimetric properties as function of Eu³⁺concentration was discussed.     

Sol-gel synthesis of single-phase Ca5MgSi3O12: Eu, Mn phosphors for white-light emitting diodes

A novel Ca₅MgSi₃O₁₂: Eu²⁺, Mn²⁺ phosphor has been prepared by a sol-gel method. X-ray diffractometer, spectrofluorometer were used to characterize structural and optical properties of the samples. The results indicate that Ca₅MgSi₃O₁₂: Eu²⁺, Mn²⁺ phosphors show two emission bands excited by ultraviolet light. Blue (around 450 nm) and green (around 502 nm) emissions originate from Mn²⁺ and Eu²⁺, respectively. With appropriate tuning the concentration ratios of Eu²⁺ to Mn²⁺, Ca₅MgSi₃O₁₂: Eu²⁺, Mn²⁺ phosphors exhibit different hues and relative color temperatures, which have potential to act as a single-phase phosphor for white-light emitting diode.     

Near-ultraviolet excitable Ca4Y6(SiO4)6O: Ce,Tb white phosphors for light-emitting diodes

The present investigation aims to demonstrate the potentiality of Tb³⁺ and Ce³⁺ co-doped Ca₄Y₆(SiO₄)₆O phosphors. By incorporation of Ce³⁺ into Ca₄Y₆(SiO₄)₆O: Tb³⁺, the excitation band was extended from short-ultraviolet to near-ultraviolet region. The energy transfer from Ce³⁺ to Tb³⁺ in Ca₄Y₆(SiO₄)₆O host was investigated and demonstrated to be a resonant type via a dipole–dipole mechanism with the critical distance of 10.2 Å. When excited by 352 nm, Ca₄Y₆(SiO₄)₆O: Ce³⁺, Tb³⁺ exhibited a brighter and broader violet-blue emission (421 nm) from the Ce³⁺ and an intense green emission (542 nm) from the Tb³⁺. Combining the two emissions whose intensities were adjusted by changing the doping levels of the co-activator, an optimized white light with chromaticity coordinates of (0.278, 0.353) is generated in Ca₄Y₆(SiO₄)₆O: 2% Ce³⁺, 8% Tb³⁺, and this phosphor could be potentially used in near-ultraviolet light-emitting diodes.     

Synthesis and photoluminescence properties of a new red emitting phosphor: Ca3(VO4)2:Eu; Mn

A new red emitting phosphor, Ca₃(VO₄)₂:Eu³⁺; Mn²⁺, was synthesized by a citric acid sol-gel combustion method and characterized by XRD, TEM and photoluminescence (PL) spectra. The red emission located at about 613 nm was ascribed to ⁵D₀-⁷F₂ transition of Eu³⁺. And the red luminescence intensity changed with annealing temperature and concentration of Eu³⁺. The effect of the co-doped Mn²⁺ was also investigated systematically.     

Synthesis and photoluminescence properties of Yb doped Ba5(PO4)3Cl phosphor for white light-emitting diodes

Yb²⁺ ion doped Ba₅(PO₄)₃Cl phosphor was synthesized by solid state reaction. Four distinct absorption bands were observed in the Ultraviolet (UV) light region due to the electronic transitions of Yb²⁺ ion from ¹S₀ ground state to ²F_5/2(t_2g), ²F_5/2(e_g), ²F_7/2(t_2g), and ²F_7/2(e_g) excited states. The main emission wavelength of the phosphor was around 630 nm. The optimized Yb²⁺ ion concentration was 0.2 mol% (λ_exc. = 400 nm). The calculated critical distance was about 8.729 Å and the concentration quenching was observed above 0.2 mol% due to the electric dipole–dipole interaction.     

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).     

A novel blue-emitting Sr3Al2O5Cl2:Ce,Li phosphor for near UV-excited white-light-emitting diodes

A novel blue-emitting Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ phosphor has been synthesized by solid state reaction. The excitation spectrum shows a broad band extending from 300 to 400 nm, and the emission spectrum shows a broad blue band peaking at 450 nm with a half width of about 100 nm. The emission intensity at 250 °C remains at about 50% of that at room temperature. The decay curve at the emission peak consists of fast and slow components. The Sr₃Al₂O₅Cl₂:Ce³⁺,Li⁺ should be a promising blue phosphor for near ultraviolet-based white-light-emitting diodes.     

Emission analysis of RE (Dy or Tb):Ca3Ln(Y,Gd)(VO4)3 powder phosphors

This paper reports on the photoluminescence results of Dy³⁺ or Tb³⁺ ions in Ca₃Ln(Y,Gd)(VO₄)₃ powder phosphors. Emission spectra of Dy³⁺:Ca₃Ln(Y,Gd)(VO₄)₃ powder phosphors have shown blue emissions (⁴F_9/2 → ⁶H_15/2) at 481 nm, yellow emissions (⁴F_9/2 → ⁶H_13/2) at 572 nm and a weak red emissions (⁴F_9/2 → ⁶H_11/2) at 661 nm upon excitation with λ_exci = 310 nm (⁶H_15/2 → ⁴L_19/2). Similarly photoluminescence spectra of Tb³⁺:Ca₃Ln(Y,Gd)(VO₄)₃ have shown green emissions (⁵D₄ → ⁷F₅) at 545 nm with λ_exci = 312 nm. For these phosphors XRD, FTIR, SEM and EDAX measurements have also been carried out.     

The synthesis and photoluminescent properties of one-dimensional ZnMoO4:Eu nanocrystals

ZnMoO₄:Eu³⁺ nanocrystals were synthesized by a mild and simple hydrothermal method. The results indicate that the pH value of the precursor solution plays a crucial role in controlling the morphology, size and structures. The leaflike, nanorods and nanowires were obtained by modulating the pH value of the precursor solution. The crystalline structure of ZnMoO₄:Eu³⁺ nanocrystals are affected by the precursor solution. The excitation and emission spectra were studied. The results indicate that relative intensity of f-f transitions to charge transfer (CT) absorption and ⁵D₀-⁷F₂ to ⁵D₀-⁷F₁ transitions greatly change in different samples.     

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.     

Optical properties of Nd-doped Ca3(VO4)2 single crystal fiber

Optical absorption and photoluminescence of Ca₃(VO₄)₂ single crystal grown by a floating-zone technique and containing Nd³⁺ ions were investigated. High absorption coefficients and broadening of most absorption bands are present at 300 K, while substructures in some of the same bands can be evidenced at 12 K. Most features of measured spectra are characteristic of random occupation of more than a single Ca²⁺ site by the Nd³⁺ ion and of distortions provoked by different charge compensation mechanisms involving oxygen vacancies promotion in the crystal lattice. Nd³⁺ optical properties were studied by using the Judd-Ofelt theory to calculate the spectral parameters relevant for laser applications.     

Synthesis process and luminescence properties of Ln doped NaY(WO4)2 nanoparticles

The hydrothermal synthesis process and luminescence properties of Ln³⁺ doped NaY(WO₄)₂ nanoparticles have been investigated. Nearly spherical Eu³⁺ doped NaY(WO₄)₂ nanoparticles can be observed. The luminescence concentration quenching of Eu³⁺ in the NaY(WO₄)₂ nanoparticles was found to be similar to that in the NaY(WO₄)₂ crystals. The upconversion luminescence intensity of the Yb³⁺-Er³⁺ codoped NaY(WO₄)₂ nanoparticles was found to be much stronger than that of the Er³⁺ doped NaY(WO₄)₂ nanoparticles.     

Luminescence properties of Ce and/or Mn activated Ca10K(PO4)7 under ultraviolet and vacuum ultraviolet excitation

New Ce³⁺ and/or Mn²⁺ activated Ca₁₀K(PO₄)₇ phosphors were prepared by solid-state reaction, and their photoluminescence properties upon ultraviolet and vacuum ultraviolet excitation were investigated. Under 254 nm excitation, a series of Ca₁₀K(PO₄)₇:xMn²⁺ samples exhibit two emission bands at 463 and 650 nm, which could be attributed to oxygen defects and ⁴T₁–⁶A₁ transition of Mn²⁺, respectively. And an energy transfer from defects to Mn²⁺ has been observed. With the Mn²⁺ content increased, the emitting hues of Ca₁₀K(PO₄)₇:Mn²⁺ can range from blue to red. By co-doping Ce³⁺ to Ca₁₀K(PO₄)₇:Mn²⁺, the emission intensity of Mn²⁺ is strongly enhanced due to an efficient energy transfer by [Ce³⁺ → Mn²⁺] and [defects → Ce³⁺ → Mn²⁺]. But under 147 nm excitation, the emission intensity of Mn²⁺ in Ca₁₀K(PO₄)₇:0.25Mn²⁺ decreases slightly compared with that in Ca₁₀K(PO₄)₇:025Mn²⁺, 0.1Ce³⁺, 0.1K⁺ due to the host sensitization competition between Ce³⁺ and Mn²⁺.     

Enhancement of red emission intensity of Ca9Y(VO4)7:Eu phosphor via Bi co-doping for the application to white LEDs

The present investigation aims at the luminescence properties of Ca₉Y(VO₄)₇:Eu³⁺, Bi³⁺ red phosphor materials. The red emission at 613 nm originating from ⁵D₀–⁷F₂ transition of Eu³⁺ in Ca₉Y(VO₄)₇ is enhanced strongly with Bi³⁺–V⁵⁺ couple as the sensitizer, under excitation either into the ⁵L₆ state or the ⁵D₂ state. The energy transfer from Bi³⁺–V⁵⁺ to Eu³⁺ is discussed. For a fixed Eu³⁺ concentration, there is an optimal Bi³⁺ concentration with 15 mol%, at which the maximum luminescence intensity of Eu³⁺ is achieved. The red emission of Ca₉Y(VO₄)₇:0.8Eu³⁺, 0.15Bi³⁺ (under 395 nm and 465 nm excitations) is stronger than that of commercial Y₂O₃:Eu³⁺ phosphor (under 395 nm and 467 nm excitations). Based on the ratios of the red emission at 613 nm to orange one at 592 nm, it is considered that the symmetry of Eu³⁺ site decreases with doping of Bi³⁺, leading to more opposite parity components. Lifetime and diffuse reflection spectra measurements indicate that the red emission enhancement is due to the enhanced transition probabilities from the ground state to ⁵L₆ and ⁵D₂ states of Eu³⁺ in the distorted crystal field. Therefore the present material is a promising red-emitting phosphor for white-light diodes with near-ultraviolet/blue GaN-based chips.     

Preparation and properties of the Pb3(VO4)2Pb3(PO4)2 system

Single crystals of the pseudobinary system Pb₃(V_1?xP_xO₄)₂ were grown via the Czochralski technique and were studied over wide ranges of x, particularly with regard to the influence of substitution on the $\text{3}\text{?}\text{mF}\text{2}\text{m}$ transition as a function of temperature.     

Hydrothermal synthesis of GdBO3:Eu nanofibres

Large-scale GdBO₃:Eu³⁺ nanofibres with uniform diameter were controllably synthesized by a glycine-assisted hydrothermal method at 170 °C using Gd(NO₃)₃, Eu(NO₃)₃ and Na₂B₄O₇·10H₂O as the precursors. X-ray diffraction (XRD) results show that the luminescent nanofibres are pure hexagonal structure and no other impurity phase appeared. Transmission electron microscopy (TEM) studies indicate that GdBO₃:Eu³⁺ has a nanofibre structure. Photoluminescence (PL) spectra results demonstrate that the GdBO₃:Eu³⁺ nanofibres have three strong ⁵D₀ → ⁷F₁ (595 nm) and ⁵D₀ → ⁷F₂ (613 and 627 nm) transition peaks corresponding to orange-red and red colors, respectively.