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.     

Self-activated afterglow luminescence of un-doped Ca2ZrSi4O12 material and explorations of new afterglow phosphors in a rare earth element-doped Ca2ZrSi4O12 system

Un-doped Ca₂ZrSi₄O₁₂ material is prepared using a solid state reaction and it emits intense green afterglow luminescence peaking at 490 nm. The afterglow luminescence can be recorded for about 4800 s (0.32 mcd m⁻²). The thermoluminescence revealed that at least four types of traps existed in the Ca₂ZrSi₄O₁₂ material and the depths of these traps were calculated. The contributions of these traps on the afterglow luminescence were also investigated in detail. Accordingly, a possible afterglow mechanism of Ca₂ZrSi₄O₁₂ was proposed. Moreover, Ca₂ZrSi₄O₁₂ was also doped by rare earth or metal ions for developmental purpose and we arrived at some useful conclusions according to the experimental results.     

Photoluminescence properties of emission-tunable Ca9Y(PO4)7: Tm,Dy phosphor for white light emitting diodes

A white-emitting Ca₉Y(PO₄)₇: Tm³⁺, Dy³⁺ phosphor has been successfully prepared by conventional high-temperature solid-state reaction. X-ray diffraction (XRD) and fluorescence spectrophotometer were used to characterize the as-synthesized phosphors. The excitation and emission spectra show that all the Tm³⁺ and Dy³⁺ co-doped Ca₉Y(PO₄)₇ samples can be effectively excited by UV light and then emit blue and yellow light simultaneously. Furthermore, the emission and color coordinate of as-obtained samples pumped by 365 nm are able to be adjusted around white light by varying the doping concentrations of Tm³⁺ and Dy³⁺. So, the as-fabricated single-composition Ca₉Y(PO₄)₇: Tm³⁺, Dy³⁺ phosphor will have a promising application in the area of white light emitting diodes.     

Persistent luminescence of SrAl2O4: Eu,Dy, Cr phosphors in the tissue transparency window

We report on the persistent luminescence of SrAl₂O₄: Eu²⁺, Cr³⁺ phosphor centered at 760 nm. The phosphor was prepared by sol-gel-combustion method. Persistent luminescence from Cr³⁺ lasted for hundreds of seconds, comparable to the long afterglow from Eu²⁺ ions in the visible region based on the continuous energy transfer from Eu²⁺ ions to Cr³⁺ ions. The introduction of Dy³⁺ ions into the phosphor further prolonged the afterglow time of Eu²⁺ and Cr³⁺ ions through the depth control of the charge traps. The optimum doping concentrations for Eu²⁺, Cr³⁺ and Dy³⁺ were 1%, 2% and 1.5%, respectively.     

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.     

Tunable color emitting of CaAl2Si2O8: Eu,Tb phosphors for light emitting diodes based on energy transfer

A series of single-phased CaAl₂Si₂O₈: Eu, Tb phosphors have been synthesized at 1400 °C via a solid state reaction. The emission bands of Eu²⁺ and Eu³⁺ were observed in the air-sintered CaAl₂Si₂O₈: Eu phosphor due to the self-reduction effect. Tb³⁺ ions that typically generated green emission were added in CaAl₂Si₂O₈: Eu phosphor for contributing for a wider-range tunable emission. Energy transfer from Eu²⁺ to Tb³⁺ and the modulation of valence distribution of Eu²⁺/Eu³⁺ that contributes to the tunable color emitting were elucidated. More importantly, a white emission can be obtained by controlling the codoped contents of Li⁺ as well as suppressing the self-reduction degree of Eu. The white light emitting with the color coordinate (0.326, 0.261) was obtained, which indicates that CaAl₂Si₂O₈: Eu, Tb is a promising tunable color phosphor for application in ultraviolet light emitting diodes (UV-LEDs).     

Novel Dy-doped Ca2Gd8(SiO4)6O2 white light phosphors for Hg-free lamps application

The luminescent properties of Ca₂Gd_8(1−x)(SiO₄)₆O₂:xDy³⁺ (1% ≤ x ≤ 5%) powder crystals with oxyapatite structure were investigated under vacuum ultraviolet excitation. In the excitation spectrum, the peaks at 166 nm and 191 nm of the vacuum ultraviolet region can be assigned to the O²⁻ → Gd³⁺, and O²⁻ → Dy³⁺ charge transfer band respectively, which is consistent with the theoretical calculated value using Jφrgensen's empirical formula. While the peaks at 183 nm and 289 nm are attributed to the f-d spin-allowed transitions and the f-d spin-forbidden transitions of Dy³⁺ in the host lattice with Dorenbos's expression. According to the emission spectra, all the samples exhibited excellent white emission under 172 nm excitation and the best calculated chromaticity coordinate was 0.335, 0.338, which indicates that the Ca₂Gd₈(SiO₄)₆O₂:Dy³⁺ phosphor could be considered as a potential candidate for Hg-free lamps application.     

Precipitation based synthesis and luminescence of Ln (Eu,Ce, Dy,Sm, Tb) activated BaCa2Si3O9-Walstromite cyclosilicate phosphors

A series of new phosphors of BaCa₂Si₃O₉:Ln³⁺, (Ln = Eu, Ce, Dy, Sm, Tb) were synthesized by precipitation based method. Good crystallinity was achieved after annealing the sample at 750 °C for 1 h in air. X-ray powder diffraction (XRD) result confirmed the formation of desired BaCa₂Si₃O₉ host. The photoluminescent excitation and emission properties of Ln³⁺, (Ln = Eu, Ce, Dy, Sm, Tb) activated BaCa₂Si₃O₉ were investigated in detail. The photoluminescence (PL) analysis of individual Ln³⁺, (Ln = Eu, Ce, Dy, Sm, Tb) activated BaCa₂Si₃O₉ phosphors exhibits interesting characteristic emission properties in their respective regions. From the measured emission spectra, Judd–Ofelt (J–O) intensity parameters (Ω₂, Ω₄, Ω₆) have been calculated and using these J–O parameters various radiative parameters such as radiative transition probabilities (A_rad), radiative lifetimes (τ_R), branching ratios (β_R) and relative quantum yield have been calculated for the studied ions.     

Sol–gel synthesis and luminescence of unexpected microrod crystalline Ca5La5(SiO4)3(PO4)3O2:Dy phosphors employing different silicate sources

Ca₅La₅(SiO₄)₃(PO₄)₃O₂ doped with Dy³⁺ were synthesized by sol–gel technology with hybrid precursor employed four different silicate sources, 3-aminopropyl-trimethoxysilane (APMS), 3-aminopropyl-triethoxysilane (APES), 3-aminopropyl-methyl-diethoxysilane (APMES) and tetraethoxysilane (TEOS), respectively. The SEM diagraphs show that there exist some novel unexpected morphological structures of microrod owing to the crosslinking reagents than TEOS as silicate source for their amphipathy template effect. X-ray pictures confirm that Ca₅La₅(SiO₄)₃(PO₄)₃O₂:Dy³⁺ compound is formed by a pure apatitic phase. The Dy³⁺ ions could emit white light in Ca₅La₅(SiO₄)₃(PO₄)₃O₂ compound, and the ratio of Y/B is 1.1, when the Dy³⁺ doped concentration is 1.0 mol%.     

Visible quantum cutting via downconversion in a novel green-emitting K2Gd(WO4)(PO4):Tb phosphor

A novel phosphor K₂Gd(WO₄)(PO₄):Tb was prepared via a solid-state reaction. The crystal structure of K₂Gd(WO₄)(PO₄) as a new host matrix for luminescence was defined to be the orthorhombic system with space group Ibca (73). Visible quantum cutting under Tb³⁺ 4f⁸–4f⁷5d¹ excitation and host excitation in K₂Gd(WO₄)(PO₄):Tb³⁺ via a downconversion was identified. In order to rationalize the quantum cutting effect, the proper mechanism was proposed. According to calculations, the quantum efficiency was up to 183.2% and 176.4% under excitation at 235 nm and 150 nm, respectively. When compared with Zn₂SiO₄:Mn²⁺ (P1-G1S), KGWP:0.5Tb³⁺ is slightly less bright over 450–650 nm but has a shorter decay time.     

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⁺.     

Investigation of near-infrared-to-ultraviolet upconversion luminescence of Tm doped NaYF4 phosphors by Yb codoping

2 mol% Tm³⁺ doped NaYF₄ phosphors with 0–98 mol% Yb³⁺ codoping were synthesized by sol–gel method. The phase transition from the mixture of hexagonal and cubic phases to single cubic phase of Tm³⁺–Yb³⁺:NaYF₄ phosphors was investigated with increasing of Yb³⁺ concentration. Near-infrared, red, blue, violet and ultraviolet upconversion emissions of Tm³⁺ were observed from the Tm³⁺–Yb³⁺:NaYF₄ phosphors under 976 nm laser diode excitation, with the strongest near-infrared to ultraviolet emissions at 20 mol% Yb³⁺ codoping. The violet and blue emissions for the ¹D₂ → ³F₄ and ¹G₄ → ³H₆ transitions of Tm³⁺ can be tuned by varying Yb³⁺ codoping concentration, which was elucidated using steady-state equations. The intensity ratio of red emissions for the ³F₂ → ³H₆ and ³F₃→³H₆ transitions of Tm³⁺ was strongly related to the Yb³⁺ codoping concentration and temperature, implying a potential application of Tm³⁺–Yb³⁺:NaYF₄ phosphors for optical temperature sensing.     

Thermally stable luminescence and energy transfer in Ce, Mn doped Sr2Mg(BO3)2 phosphor

Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺ and Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors have been synthesized by conventional solid state reaction technology at 900 °C for 12 h in reducing atmosphere. The phase purity, photoluminescence (PL) properties, thermal stability, energy transfer and luminescent decay curves have been investigated. Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ phosphors show blue and deep-red¹ emission bands. The deep-red emission band is attributed to the energy transfer from Ce³⁺ to Mn²⁺. The fluorescence lifetimes of Ce³⁺ in co-doped sample are shorter than that in single doped one, which confirms that the energy transfer takes place. The phosphors have weak thermal quenching. The luminescence properties of Sr₂Mg(BO₃)₂:Ce³⁺,Li⁺,Mn²⁺ make the phosphor a new bicolor emitting material.     

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.     

Synthesis and the luminescent properties of europium-activated Ca2SnO4 phosphors

The synthesis and photoluminescent (PL) properties of calcium stannate crystals doped with europium grown by mechanically activated in a high energy vibro-mill have been investigated. The characteristics of Ca₂SnO₄:Eu³⁺ phosphors were found to depend on the amounts of europium ions. The XRD profiles revealed that the system, (Ca_1−xEu_x)₂SnO₄, could form stable solid solutions in the composition range of x = 0–7% after being calcined at 1200 °C. The calcined powders emit bright red luminescence centered at 618 nm due to ⁵D₀ → ⁷F₂ electric dipole transition. Both XRD data and the emission ratio of (⁵D₀ → ⁷F₂)/(⁵D₀ → ⁷F₁) reveal that the site symmetry of Eu³⁺ ions decreases with increasing doping concentration. The maximum PL intensity has been obtained for 7 mol% concentration of Eu³⁺ in Ca₂SnO₄.     

Photoluminescence properties of MgAl2O4:Dy powder phosphor

Trivalent dysprosium (Dy³⁺) activated magnesium alluminate phosphors were synthesized by high temperature solid state reaction method. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting phosphors. The results show that the obtained MgAl₂O₄:Dy³⁺ phosphors have good crystallinity, spherical morphology with sizes ranged from 120 to 140 nm and strong blue emission under an excitation of 258 nm. The emission spectrum of this phosphor consists of two emission bands: blue band and yellow band, and the emission intensity of the former is stronger than that of the later. Luminescence quenching is explained and the corresponding luminescence mechanisms have been proposed.     

Electron–vibrational interaction in 5d state of Ce ion in (LiMg/Li2Na/Li3)BF6 phosphors

The electron–vibrational interaction (EVI) parameters such as Huang–Rhys factor, effective phonon energy and zero phonon line position were estimated using data from our recent reported work, on photoluminescence in rare earth doped complex hexafluorides phosphors LiMgBF₆, Li₂NaBF₆ and Li₃BF₆ Validity of results were established by modeling the emission line which was found to be in good agreement with experimental photoluminescence spectra.     

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.     

Study on the effect of apatite structure on spectroscopic properties of bismuth activated alkaline earth metal chlorophosphate [M5(PO4)3Cl; M = Ca,Sr and Ba]

The luminescent properties of Bi activated M₅(PO₄)₃Cl (M = Ca, Sr and Ba) prepared under the air and mild reducing conditions (5% H₂ and 95% N₂) were investigated. Results show that all samples present ultraviolet (UV) emissions of Bi³⁺ besides Ba₅(PO₄)₃Cl prepared in reducing condition, which also shows broadband yellow–white and near infrared (NIR) luminescence attributed to univalent bismuth (Bi⁺). Emission data with the size available lattice sites of samples prepared in air suggests there are two types of Bi luminescent center, and each located in one of the two available M²⁺ lattice sites. In the case of Ba₅(PO₄)₃Cl crystal, Bi³⁺ incorporated on Ba²⁺(1) sites can be reduced to Bi⁺ for reasons of charge compensation and size match of ionic radius.     

Sol-gel synthesis and green upconversion luminescence in BaGd2(MoO4)4:Yb,Er phosphors

Yb³⁺/Er³⁺ codoped BaGd₂(MoO₄)₄ phosphor powders were prepared by the Sol-gel method and the upconversion luminescence properties were investigated in detail. Under 980 nm semiconductor laser excitation, BaGd₂(MoO₄)₄:Yb³⁺,Er³⁺ phosphor exhibits green upconversion luminescence with peaks at 530 and 550 nm, which are due to the transitions of Er³⁺ (²H_11/2) → Er³⁺ (⁴I_15/2) and Er³⁺ (⁴S_3/2) → Er³⁺ (⁴I_15/2), respectively. Both of the two green emission lines are produced by populating Er³⁺ ions to the excited state through a two-photon process. By monitoring the intensities of the green upconversion luminescence, the optimum conditions for the Sol-gel synthesis were determined when the molar ratio of citric acid to total chelate metal cations was 2:1 and the sintering temperature was at 1073 K. The concentration quenching effect for Er³⁺ was found at the optimum doping concentration of 6 mol%, and the critical distance for the neighboring Er³⁺ was determined to be about 21.5 Å.