Synthesis and photoluminescence properties of the high-brightness Eu3+-doped Sr3Bi(PO4)3 phosphors

A series of orange reddish emitting phosphors Eu³⁺-doped Sr₃Bi(PO₄)₃ have been successfully synthesized by conventional solid-state reaction, and its photoluminescence (PL) properties have been investigated. The excitation spectra reveal strong excitation bands at 392 nm, which match well with the popular emissions from near-UV light-emitting diode chips. The emission spectra of Sr₃Bi(PO₄)₃:Eu³⁺ phosphors invariably exhibit five peaks assigned to the ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) transitions of Eu³⁺ and have dominating emission peak at 612 nm under 392 nm excitation. The luminescence intensity was enhanced with increasing Eu³⁺ content and the emission reached the maximum intensity at x=0.05 in Sr₃Bi(PO₄)₃:xEu³⁺. The energy transfer behavior in the phosphors was discussed. The Commission Internationale de lEclairage (CIE) chromaticity coordinates, the quantum efficiencies, and the decay curves of the entitled phosphors excited under 392 nm are also investigated. The experimental results indicate that the Eu³⁺-doped Sr₃Bi(PO₄)₃ phosphors are promising orange reddish-emitting phosphors pumped by near-UV light.     

Synthesis,photoluminescence and thermoluminescence properties of LiNa3P2O7:Tb3+ green emitting phosphor

The alkaline phosphate based LiNa₃P₂O₇:Tb³⁺ phosphors are prepared by solid state reaction method. X-ray diffraction (XRD) analysis shows that all the powders possess orthorhombic structure. Fourier transform infrared (FTIR) spectroscopy studies suggest that the phosphor belong to the diphosphate family. The morphology of the phosphors is identified by scanning electron microscopy (SEM). Upon 378 nm excitation, the LiNa₃P₂O₇:Tb³⁺ phosphors shown emission bands at 482, 545, 588 and 620 nm corresponding to the transitions ⁵D₄→⁷F₆, ⁵D₄→⁷F₅, ⁵D₄→⁷F₄ and ⁵D₄→⁷F₃, respectively. The optimized concentration of Tb³⁺ in LiNa₃P₂O₇ phosphor is found to be 9 mol%. The concentration quenching mechanism was proved to be the exchange interaction between two nearest Tb³⁺ ions with the critical distance (R_c) of 1.18 nm. The Commission International de l'Eclairage (CIE) coordinates evidence that the phosphors emit in the green light region. Thermoluminescence properties of the prepared phosphors are studied by pre-irradiating the powders with different doses of UV irradiation. The kinetic parameters of TL glow curves are calculated using Chen's peak shape method.     

Enhanced UVB emission and analysis of chemical states of Ca5(PO4)3OH:Gd3+,Pr3+ phosphor prepared by co-precipitation

Hydroxyapatite (Ca₅(PO₄)₃OH) is a well-known bioceramic material used in medical applications because of its ability to form direct chemical bonds with living tissues. This mineral is currently used as a host for rare-earth ions (e.g. Gd³⁺, Pr³⁺, Tb³⁺, etc.) to prepare phosphors that can be used in light emitting devices of different types. In this study Ca₅(PO₄)₃OH:Gd³⁺,Pr³⁺ phosphors were prepared by the co-precipitation method and were characterised by x-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy, energy dispersive x-ray spectroscopy and photoluminescence spectroscopy. The x-ray diffraction pattern was consistent with the hexagonal phase of Ca₅(PO₄)₃OH referenced in JCPDS card number 73-0293. The x-ray photoelectron spectroscopy data indicated that Ca²⁺ occupied two different lattice sites, referred to as Ca1 and Ca2. The photoluminescence data exhibited a narrowband emission located at 313 nm, which is associated with the ⁶P_7/2→⁸S_7/2 transition of the Gd³⁺ ion. This emission is classified as ultraviolet B and it is suitable for use in phototherapy lamps to treat various skin diseases. The photoluminescence intensity of the 313 nm emission was enhanced considerably by Pr³⁺ co-doping.     

Hydrothermal preparation and luminescence property of MWO4:Sm3+ (M = Ca,Sr, Ba) red phosphors

MWO₄:Sm³⁺ (M = Ca, Sr and Ba) red phosphors with spherical microparticles were successfully prepared via a mild and facile hydrothermal route. The crystal structure and particle morphology were investigated by the X-ray diffraction (XRD) and scanning electron microscope (SEM), respectively. Photoluminescence excitation and emission spectra and decay curve were used to characterize the luminescence properties of the MWO₄:Sm³⁺ phosphors. The excitation spectra indicate that MWO₄:Sm³⁺ phosphors can be excited effectively by the UV InGaN light-emitting diode (LED), and the emission spectra show that the phosphors can emit strong red light from 600 to 650 nm. Therefore, it is considered to be a new promising red phosphor for white LED application.     

Luminescent properties of Eu3+ and Sm3+ activated M2SiO4 (M=Ba,Sr and Ca) red-emitting phosphors for WLEDs

Eu³⁺ and Sm³⁺ activated M₂SiO₄ (M=Ba, Sr and Ca) red-emitting phosphors were synthesized by a solid state reaction. The results of XRD and SEM measurements show that the samples are single phase and have irregular shape. The excitation and emission spectra indicate that these phosphors were effectively excited by ultraviolet (395 nm) and blue (466 nm) light and exhibited red performance. The charge compensator R⁺ (R⁺=Li⁺, Na⁺ and K⁺) injecting into the host efficiently enhanced the luminescence intensity of the M₂SiO₄: Eu³⁺ and M₂SiO₄: Sm³⁺ phosphors. The emission intensity of M₂SiO₄: Eu³⁺ and Sm³⁺ doping Li⁺ were higher than that of Na⁺ or K⁺.     

Spectral structure of barium–phosphate–silicate phosphor Ba10(PO4)4(SiO4)2:EuM+

The new apatite–silicate phosphor doped with Eu ions in Ba₁₀(PO₄)₄(SiO₄)₂ matrix was synthesized through solid-state reaction. It was found that the as-synthesized phosphor displayed apparent mixture of band and line emission peaks giving rise to pseudo white light. The narrow emission bands peaking at 410 nm can be assigned to the 4f⁶5d→4f⁷(⁸S_7/2) transition of Eu²⁺ ions, and the other band at 507 nm is ascribed to anomalous fluorescent emission. One group of line emission peaking at 595 nm and 613 m were due to the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ions. The occurrence of photostimulated luminescence and discrete emission lines in violet (410 nm), green (507 nm) and red (595 nm and 613 nm) colors indicate that this material has potential application in fields of white-light-emitting.     

A reddish orange-emitting stoichiometric phosphor K3Eu(PO4)2 for white light-emitting diodes

A series of Eu³⁺ activated K₃Y_1?xEu_x(PO₄)₂ phosphors were synthesized by the solid-state reaction method. The structures and photoluminescent properties of these phosphors were investigated at room temperature. The results of XRD patterns indicate that these phosphors are isotypic to the monoclinic K₃Y(PO₄)₂ or K₃Eu(PO₄)₂. The excitation spectra indicate that these phosphors can be effectively excited by near UV (370–410 nm) light. The orange emission from transition ⁵D₀–⁷F₁ is dominant, and the peak value ratio of ⁵D₀–⁷F₁/⁵D₀–⁷F₂ is 1.44. The emission spectra exhibit strong reddish orange performance (CIE chromaticity coordinates: x=0.63, y=0.36), which is due to the ⁵D₀–⁷F_J transitions of Eu³⁺ ions. The relationship between the structure and the photoluminescent properties of the phosphors was studied. The absence of concentration quenching of Eu³⁺ was observed in K₃Y_1?xEu_x(PO₄)₂. K₃Eu(PO₄)₂ has potential application as a phosphor for white light-emitting diodes.     

Luminescent properties of Eu2+and Dy3+ ions in Ba4Al2O7 phosphor for solid state lighting

In this paper we report the combustion synthesis of rare earth (RE=Eu, Dy) doped Ba₄Al₂O₇ phosphors. Prepared phosphors were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), CIE color co-ordinates and their photoluminescence (PL) properties were also investigated. In case of Ba₄Al₂O₇: Eu²⁺, the emission spectra show unique band centered at 495 nm, which corresponds to the 4f⁶5d¹→4f⁷ transition of Eu²⁺, and PL emission spectra of Dy³⁺ ion under 348 nm excitation give two bands centered at 478 nm (blue) and 575 nm (yellow), which originate from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The results indicate that the Eu²⁺ and Dy³⁺ activated Ba₄Al₂O₇ phosphor could find application in solid state lighting.     

Synthesis and characterization of fast-decaying bluish green phosphors of Tb3+-doped CaSi2O2N2 for 2D/3D plasma display panels

Oxynitride phosphor powders comprising of CaSi₂O₂N₂ doped with Tb³⁺ were successfully synthesized using a high-temperature solid-state reaction method. The experimentally determined photoluminescence (PL) properties of the produced phosphors meet the requirements of 2D/3D plasma display panels (PDPs). In particular, under the excitation of vacuum ultraviolet (VUV) synchrotron radiation and ultraviolet (UV) irradiation, emission peaks corresponding to the ⁵D₃→⁷F_J (J=6, 5, 4, 3) and ⁵D₄→⁷F_J (J=6, 5, 4, 3) transitions of Tb³⁺ ions were recorded. Monitoring the ⁵D₄→⁷F₅ emission of Tb³⁺ at 545 nm, the excitation bands were assigned to the host-related absorption as well as the 4f–5d (fd) and the 4f–4f (ff) transitions of Tb³⁺. The produced phosphors can be efficiently excited at 147 nm, and have an adequately short decay time (τ_1/10=1.14 ms).     

Photoluminescence characterization of a novel red-emitting phosphor In2(MoO4)3:Eu3+ for white light emitting diodes

The red-emitting phosphor In₂(MoO₄)₃:Eu³⁺ with cubic crystal structure was synthesized by a conventional solid-state reaction technique and its photoluminescence properties were investigated. The prepared phosphor can be efficiently excited by ultraviolet (395 nm) and blue (466 nm) light. The emission spectra of the phosphor manifest intensive red-emitting lines at 612 nm due to the electric dipole ⁵D₀→⁷F₂ transitions of Eu³⁺. The chromaticity coordinates of x=0.63, y=0.35 (λ_ex=395 nm) and x=0.60, y=0.38 (λ_ex=466 nm) are close to the standard of National Television Standard Committee values (NTSC) values. The concentration quenching of In₂(MoO₄)₃:Eu³⁺ is 40 mol% and the concentration self-quenching mechanism under 466 nm excitation was the dd intereaction. As a result of the strong emission intensity and good excitation, the phosphor In₂(MoO₄)₃:Eu³⁺ is regarded as a promising red-emitting conversion material for white LEDs.     

Luminescent properties and energy transfer of double-emitting NaSrPO4:Eu2+,Tb3+ phosphor for near-UV white LEDs

Novel blue/green NaSrPO₄ phosphors co-doped with Eu²⁺ and Tb³⁺ were synthesized by a conventional solid-state reaction. Their luminescent properties were characterized by using powder X-ray diffraction, photoluminescence excitation and emission spectra, lifetime, and temperature dependent emission spectra, respectively. The NaSrPO₄:Eu²⁺,Tb³⁺,Na⁺ phosphor showed an intense broad excitation band between 250 and 430 nm, which was in agreement with the near-UV chip (350–420 nm), and it exhibited two dominating emission bands at 445 and 545 nm, corresponding to the allowed 4f⁶5d¹→4f⁷(⁸S_7/2) transition of Eu²⁺ ion and the ⁵D₄→⁷F₅ transition of Tb³⁺ ion, respectively. The emission intensity and lifetime of Eu²⁺ ion decreased with the increasing concentration of Tb³⁺ ion, which strongly indicated that an effective energy transfer occurred from Eu²⁺ to Tb³⁺ in NaSrPO₄ host. The principle of the energy transfer should be the combined effect of the non-radiative resonant energy transfer and the phonon-assisted non-radiative process.     

Development of zeolite-derived novel aluminosilicate phosphors

In this research, zeolite-derived aluminosilicate phosphors were synthesized through the ion exchange route. Red light-emitting property of Eu³⁺-doped aluminosilicate phosphors were discussed from a view point of the Eu content, heat-treatment condition and the oxidation state of Eu ions. The crystalline phase of the host aluminosilicates could be successfully controlled as designed based on the published NaAlO₂–SiO₂ binary phase diagram. Orange-red emission peaks derived from the ⁵D₀→⁷F_j (j=0, 1, 2, 3, 4) transition of Eu³⁺ were observed around 590–700 nm, and 4f⁶5d→4f⁷ transition of Eu²⁺ was observed at around 400–500 nm. The relative intensity I(⁵D₀→⁷F₂) of the dominant emission peak at 612 nm increased consistently with the Eu content. The results of the XANES spectroscopy analysis revealed that Eu²⁺ ion in the 1400 °C as heat-treated host aluminosilicate were successfully converted to Eu³⁺ by the additional annealing at 1100 °C. The Eu contents and heat-treatment conditions were determined to exhibit the best performance as a red phosphor, which were 10 wt% and 1500 °C, respectively     

Dual color emitting Eu doped strontium orthosilicate phosphors synthesized by bio-template assisted ultrasound for solid state lightning and display applications

A novel Sr₂SiO₄:Eu (1–5 mol %) superstructures (SS) were synthesized using bio-sacrificial A.V. gel assisted ultrasound method. Powder X-ray diffraction patterns confirmed the presence of both α and β phase formation. It was evident that the morphological growth was highly reliant on A.V. gel concentration, sonication time, pH and sonication power. The formation mechanisms for different hierarchical SS were proposed. From diffuse reflectance spectra, the energy band gap was estimated and found to be ∼4.70–5.11 eV. The photoluminescence emission spectra for the excitation at 392 nm, shows characteristic emission peaks at 593, 613, 654 and 702 nm which were attributed to ⁵D₀ → ⁷F₀, ⁷F_1, ⁷F₂ and ⁷F₃ transitions of Eu³⁺ ions respectively. Conversely, when the samples were subjected to the heat treatment at 850 °C for 3 h under argon atmosphere, display an intense broad emission peak with two de-convoluted peaks at 490 and 550 nm due to 4f⁶5d¹→4f¹ (⁸S_7/2) transitions of Eu²⁺ ions. The concentration quenching phenomenon was discussed which attributes to energy transfer, electron–phonon coupling and ion–ion interaction. The Judd–Ofelt intensity parameters and other radiative properties were estimated by using emission spectra. The CIE chromaticity coordinate values of Sr₂SiO₄:Eu²⁺ and Eu³⁺ nanophosphors were located in green and red regions respectively. The calculated CCT and CRI values specify that the present phosphor can be fairly useful for both green and red components of white LED’s. Luminescence decay and quantum yield suggest the suitability of this phosphor as an efficient luminescent medium for light emitting diodes. Overall, the results elucidated a rapid, environmentally benign, cost-effective and convenient method for Sr₂SiO₄:Eu³⁺ synthesis and for the possible applications such as solid state lighting and display devices.     

A potential red-emitting phosphor with high color-purity for near-UV light emitting diodes

New red tungstates phosphors, Na₅La_1?xLn_x(WO₄)₄ (Ln = Eu, Sm) and Na₅Eu_1?xSm_x(WO₄)₄, were prepared by solid-state reaction technique. And their structure and photo-luminescent properties were investigated. The introduction of Sm³⁺ broadened the excitation band around 400 nm of the phosphors, and strengthened the red emission. And the possible energy transfer process from Sm³⁺ to Eu³⁺ is discussed. The single red LED was fabricated by combining InGaN chip with Na₅Eu_0.94Sm_0.06(WO₄)₄ as red phosphor, intense red light can be observed by naked eyes. Then the phosphor Na₅Eu_0.94Sm_0.06(WO₄)₄ may be a good candidate for red component of near-UV InGaN-based W-LEDs, because of efficient red-emitting with broadened absorption around 400 nm and appropriate CIE chromaticity coordinates (x = 0.65, y = 0.34).     

Microwave sol-gel process of KGd(WO4)2:Ho3+/Yb3 phosphors and their upconversion photoluminescence properties

Double tungstate KGd_1−x(WO₄)₂:Ho³⁺/Yb³⁺ phosphors with doping concentrations of Ho³⁺ and Yb³⁺ (x=Ho³⁺+Yb³⁺, Ho³⁺=0.05, 0.1, 0.2 and Yb³⁺=0.2, 0.45) were successfully synthesized by the microwave sol–gel method, and the upconversion mechanisms were investigated in detail. The synthesized particles formed after heat-treatment at 900 °C for 16 h showed a well crystallized morphology with particle sizes of 2–5 μm. Under excitation at 980 nm, the UC intensities of KGd_0.7(WO₄)₂:Ho_0.1Yb_0.2 and KGd_0.5(WO₄)₂Ho_0.05Yb_0.45 particles exhibited yellow emissions based on a strong 550-nm emission band in the green region and a strong 655-nm emission band in the red region, which were assigned to the ⁵S₂/⁵F₄→⁵I₈ and ⁵F₅→⁵I₈ transitions, respectively. The Raman spectra of the doped particles indicated the presence of strong peaks at higher frequencies of 764, 812, 904, 984, 1050, 1106, 1250 and 1340 cm⁻¹ induced by the disorder of the [WO₄]²⁻ groups with the incorporation of the Ho³⁺ and Yb³⁺ elements into the crystal lattice or by a new phase formation.     

Synthesis and photoluminescence properties of YVO4:Eu3+, Al3+ phosphor

The Y_0.95?xAl_xVO₄:5%Eu³⁺ (0≤x≤0.1) phosphors were successfully synthesized by solid state reaction at 900 °C for 6 h, and their luminescence properties were investigated under UV and VUV excitation. Monitoring at 619 nm, a strong broad absorption was enhanced by co-doping of Al³⁺ into the YVO₄:Eu³⁺ lattices at 256 nm under UV excitation. The VUV excitation spectra also showed the enhanced excitation bands at about 156 and 200 nm. Under 254 or 147 nm excitation, it was found that Y_0.95?xAl_xVO₄:Eu³⁺(0≤x≤0.1) phosphors showed strong red emission at about 619 nm corresponding to the electric dipole ⁵D₀^–7F₂ transition of Eu³⁺. The improvement of luminescence intensity of YVO₄:Eu³⁺ was also observed after partial substituting Y³⁺ by Al³⁺ and the optimal luminescence intensity appeared with incorporation of 2.5 mol% Al³⁺.     

Photoluminescence investigations of Li2SiO3:Ln (Ln=Er3+, Eu3+, Dy3+, Sm3+) phosphors

In this study, we report a comprehensive structural and photoluminescence (PL) study on lithium metasilicate (Li₂SiO₃) phosphor ceramics doped with four rare earth (RE) ions. X-ray diffraction (XRD) patterns show a dominant phase, characteristic of the orthorhombic structure Li₂SiO₃ compound and the presence of dopants has no effect on the basic crystal structure of the material. The first excited state Er³⁺ luminescence at 1.54 μm arises from a sharp atomic-like radiative transition between the ⁴I_13/2 state and the ⁴I_15/2 state (ground level) under a 532 nm line of an Ar ion laser excitation. Sm doped samples showed Sm³⁺ emission characteristics corresponding to the some ⁴G_5/2→⁶H_j (j=5/2,9/2,11/2) transitions indicating a strong crystal-field effect. PL spectra of Eu doped material exhibited peaks corresponding to the ⁵D₀→⁷F_j (j=0,1,2,3 and 4) transitions under 405 nm excitation. The dominant red color emission at 612 nm from the hypersensitive (⁵D₀→⁷F₂) transition of Eu³⁺ indicates the inversion antisymmetry crystal field around Eu³⁺ ion, which is favorable to improve the red color purity. Dy doped samples showed the Dy³⁺ emission characteristic due to the ⁴F_9/2→⁶H_13/2 transition. Their relative intensity ratios also suggested the presence of a symmetric environment around the metal ion. We suggest that lithium metasilicate has enough potential candidates to be a phosphor material.     

Zinc silicates with tunable morphology by surfactant assisted sonochemical route suitable for NUV excitable white light emitting diodes

The cationic surfactants assisted ultrasound route was used to prepare Dy³⁺ doped Zn₂SiO₄ nanophosphors. The final products were characterized by powder X-ray diffraction (PXRD), ultraviolet visible spectroscopy, scanning electron microscopy, transmission electron microscopy and photoluminescence. Orthorhombic phase of Zn₂SiO₄:Dy³⁺ (JCPDS card No. 35-1485) was confirmed from PXRD. It was evident that the morphology of spherical and broom like structures were obtained with epigallocatechin gallate (EGCG) and cetyltrimethylammonium bromide (CTAB) surfactants respectively. Further the size and agglomeration of the products were varied with surfactants concentration, sonication time, pH and sonication power. The probable formation mechanisms to obtain various micro/nano superstructures were discussed. The characteristic PL peaks were observed at 484, 574 and 666 nm due to the electronic transitions ⁴F_9/2 → ⁶H_j (j = 15/2, 13/2, 11/2) of Dy³⁺ ions upon excited at NUV pumping wavelength of 350 nm [⁶H_15/2 → ⁶P_7/2 (⁴M_15/2)]. The Judd–Ofelt intensity parameters and radiative properties were estimated by using PL emission data. The photometric studies indicated that the obtained phosphors could be promising materials in white light emitting diodes (wLED’s). The present synthesis route was rapid, environmentally benign, cost-effective and useful for industrial applications such as solid state lighting and display devices.     

Novel EGCG assisted ultrasound synthesis of self-assembled Ca2SiO4:Eu3+ hierarchical superstructures: Photometric characteristics and LED applications

This paper reports for the first time ultrasound, EGCG assisted synthesis of pure and Eu³⁺ (1–5 mol%) activated Ca₂SiO₄ nanophosphors having self-assembled superstructures with high purity. The shape, size and morphology of the product were tuned by controlling influential parameters. It was found that morphology was highly dependent on EGCG concentration, sonication time, pH and sonication power. The probable formation mechanism for various hierarchical superstructures was proposed. The PL studies of Ca₂SiO₄:Eu³⁺ phosphors can be effectively excited by the near ultraviolet (UV) (396 nm) light and exhibited strong red emission around 613 nm, which was attributed to the Eu³⁺ (⁵D₀ → ⁷F₂) transition. The concentration quenching phenomenon was explained based on energy transfer between defect and Eu³⁺ ions, electron–phonon coupling and Eu³⁺–Eu³⁺ interaction. The Judd–Ofelt intensity parameters and radiative properties were estimated by using PL emission spectra. The photometric studies indicate that the obtained phosphors could be a promising red component for possible applications in the field of white light emitting diodes.     

Near infrared and charge transfer luminescence of trivalent ytterbium in KLa(PO3)4 powders

The polycrystalline powders of condensed polyphosphates KLa_(1 ? x)Yb_x(PO₃)₄ (x = 5, 10, 15, 20%) with linear chain were prepared by solid-state reaction. These samples were characterized by X-ray diffraction, FTIR and Raman scattering spectroscopies. The obtained powders are formed by single monoclinic phase of type III of condensed polyphosphate KLa(PO₃)₄ (KLP) crystallized with P2₁ space group. Lattice parameters varied as a function of the ytterbium concentration. As the Yb³⁺ concentration increased, the crystal lattice parameters were decreased. For the first time, near infrared (NIR) and UV–Visible spectroscopy of Yb³⁺ in KLa(PO₃)₄ powders, at room temperature, are carried out. In the IR range, a broad band relative to the fundamental ²F_5/2 → ²F_7/2 emission was registered. In the UV–Visible spectra, two bands typical of the Yb³⁺ charge transfer band (CTB) luminescence are observed. The registered decay times of these two emission types showed low sensibility to the Yb³⁺ concentration in KLa(PO₃)₄.