Influence of small additives of rare-earth elements on the structure of fluorophosphate glasses

The physicochemical properties and Raman spectra of glasses of the composition 40Ba(PO₃)₂ · 60MgCaSrBaAl₂F₁₄ doped with europium and terbium have been investigated. The results of the performed investigations have been compared with the data of the analysis of the recorded EPR spectra of irradiated glasses of the same compositions in terms of the model of the effective capture volume and with the luminescence data available in the literature. The concentration ranges of terbium and europium ions (0.05–0.10) mol % or (0.7–1.3) × 10¹⁹ ions/cm³, in which these ions retain the oxygen environment according to the analysis of the studies carried out by different methods, are in satisfactory agreement. The dependence of the local environment of rare-earth ions in fluorophosphate glasses on their concentration has been established.     

Dependence of the Spectroscopic Properties of Europium on the Spatial Distribution of Rare-Earth Ions in Fluorophosphate Glasses

Doped fluorophosphate glasses containing 4–13 mol % Ba(PO₃)₂ have been studied. Analysis of the Raman spectra has revealed that the structure of glasses containing up to 1 mol % Ba(PO₃)₂ involves isolated [PO₄] tetrahedra. An increase in the Ba(PO₃)₂ content brings about the formation of pyrophosphate groups, which are dominant in the glass containing 11 mol % Ba(PO₃)₂. The introduction of up to 2 mol % EuF₃ into the glasses containing 5 and 7 mol % Ba(PO₃)₂ leads to a decrease in the Landau-Placzek ratio. This is interpreted within the model of segregation of dopant ions. From analyzing the induced absorption spectra, the content of Eu³⁺ ions with a predominantly phosphate environment is estimated at ∼0.005 mol %. It is shown that, for the glasses containing 4 mol % Ba(PO₃)₂, the intensity ratio of the Eu³⁺ luminescence bands attributed to the ⁵ D ₀-⁷ F ₁ and ⁵ D ₀-⁷ F ₂ transitions changes with an increase in the EuF₃ content from 0.01 to 2.0 mol %. This dependence of the intensity ratio on the EuF₃ content exhibits a maximum at 0.5 mol % EuF₃, which is explained by the change in the local environment of the rare-earth ion.Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Bocharova, Karapetyan, Mironov, Tagil’tseva, Yanush.     

Study of Eu3+–Gd3+ co-doped Ba–Bi–B glasses for red-laser applications: Physical,structural, photoluminescence and time-resolved spectral characteristics

A series of Eu³⁺ and Eu³⁺/Gd³⁺ co-doped barium-bismuth-borate (Ba–Bi–B) glasses were prepared by melt-quench technique. And deliberated the physical, structural, and spectroscopic properties of all glasses and explored the energy transfer process from Gd³⁺ to Eu³⁺ ions. The density of glasses increased with increasing of Gd³⁺ concentration in co-doped glasses. Characteristics of steady-state and time-resolved photoluminescence (PL) of Eu-doped and Eu³⁺-Gd³⁺ co-doped glasses under different excitation wavelengths suggested the prospects of the investigated glass system for display device applications. PL spectrum displays a strong red emission peak centered at 612 nm due to the Eu³⁺: ⁵D₀→ ⁷F₂ transition. Less intense emissions centered at 577 nm (⁷F₀), 590 nm (⁷F₁), 651 nm (⁷F₃) and 700 nm (⁷F₄) are also observed from the radiative transitions of the excited state ⁵D₀ of Eu³⁺ions. The values of radiative parameters such as transition probability, branching ratios, and stimulated emission cross-sections were obtained from Judd–Ofelt theory analysis and indicated the aptness of the Ba–Bi–B glasses for optical devices. A 5-fold enhancement in the PL intensity was observed in 1.0 mol% Eu³⁺ and 3.0 mol% Gd³⁺ co-doped glass under λ_Exci. = 394 nm excitation. The calculated commission Internationale de l'eclairage color coordinates and correlated color temperature values show that the Ba–Bi–B glasses are useful for red-laser and display device applications.     

Structural-microstructural characterization and optical properties of Eu3+,Tb3+-codoped LaPO4·nH2O and LaPO4 nanorods hydrothermally synthesized with microwaves

Rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·nH₂O single-crystal nanorods with the compositions La_0.99999-xEu_xTb_0.00001PO₄·nH₂O (x?=?0–0.03), La_0.99999-yTb_yEu_0.00001PO₄·n′H₂O (y?=?0–0.010), and La_0.99999-zTb_zEu_0.000007PO₄·n′′H₂O (z?=?0–0.012) were hydrothermally synthesized with microwaves. It is shown that the Eu³⁺,Tb³⁺ codoping does not affect the thermal stability of these nanorods, which is due to the formation of substitutional solid solutions with both Eu³⁺ and Tb³⁺ replacing La³⁺ in the crystal lattice. Moreover, it is also shown that monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ single-crystal nanorods can be obtained by calcining their rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄·(n,n′ or n′′)H₂O counterparts at moderate temperature in air, and that they are thermally stable. It is also observed that, for the same Eu³⁺,Tb³⁺-codoping content, the monazite-type Eu³⁺,Tb³⁺-codoped LaPO₄ nanorods exhibit higher photoluminescent efficiency than the rhabdophane-type Eu³⁺,Tb³⁺-codoped LaPO₄· (n,n′ or n′′)H₂O nanorods. Moreover, it is found that the highest photoluminescence emission corresponds to the monazite-type La_0.96999Eu_0.02Tb_0.00001PO₄ nanorods for the La_0.99999-xEu_xTb_0.00001PO₄ system. However, for those compositions energy transfer from Tb³⁺ to Eu³⁺ does not occur. In addition, for an efficient energy transfer to occur, a content of at least 1?mol% Tb³⁺ is needed in all the studied materials.     

A model of the capture volume of free carriers in fluorophosphate glasses doped with terbium

The induced electron paramagnetic resonance (EPR) and optical absorption spectra of Tb₂O₃-doped glasses in the LiF-MgF₂-Ba(PO₃)₂ system are investigated. The intensities of the doublet signals from PO ₄ ^2– and PO ₃ ^2– centers in regions with different contents of the fluoride component are determined as functions of the terbium concentration. It is shown that fluorophosphate glasses can be characterized by two values of the capture volume parameter, which differ by a factor of 5.0–6.6 depending on the dopant concentration. In the range of minimum dopant concentrations at which the capture volume is maximum, the dopant ions have a hypothetically phosphate environment. It is suggested that the capture volume parameter defined by the expression lnc/c ₀ = –VC ₃ can be treated as a characteristic of the distribution of dopant ions in fluorophosphate glasses.Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Bocharova.     

Luminescence properties of Eu3+- and Tb3+-doped δ-Bi2O3 stabilized by Th4+ substitution

The extent of incorporating Eu³⁺ and Tb³⁺ for bismuth in the oxygen-deficient fluorite structured Bi_0.50Th_0.50O_y has been examined together with the comprehension of their luminescence characteristics. The samples were synthesized by solution combustion method from which doping limits of Eu³⁺ and Tb³⁺, respectively, in the fluorite structure was determined. Uniform distribution of constituent elements was confirmed from elemental mapping. Doping Eu³⁺ and Tb³⁺-ions introduced compressive strain and oxygen vacancies in the system. Raman spectra of doped samples confirmed the fluorite structure and revealed the existence of oxygen vacancies in them. While Tb-doped samples showed a systematic decrease in band gap with increase in dopant concentration, such systematic variation was not observed for Eu-doped samples. Conclusions about the local site symmetry around Eu³⁺ and Tb³⁺ ions in the defect fluorite structure have been drawn from the photoluminescent spectral analysis of doped samples. Energy transfer from Bi³⁺ to Eu³⁺ and Tb³⁺-has been observed in these samples. The Judd-Ofelt analysis has been carried out to understand luminescence characteristics in these samples.     

Emission analysis of CdO–Bi2O3–B2O3 glasses doped with Eu and Tb

This article reports on the emission properties of cadmium bismuth borate (CdBiB) glasses as a function of doping concentrations of Eu³⁺ and Tb³⁺ ions. The functional groups present in the glasses have been identified by analyzing FT-IR spectra. The emission spectra of Eu³⁺ and Tb³⁺:CdBiB glasses have shown reddish green emissions at 616 nm (⁵D₀→⁷F₂) under the excitation at 465 nm and at 547 nm (⁵D₄→⁷F₅) under the excitation at 485 nm, respectively. The Judd–Ofelt (J–O) theory was applied to evaluate the J–O intensity parameters from the absorption and the emission spectra; by using the J–O intensity (Ω_λ) parameters, spontaneous emission transition probability (A), total radiative transition rate (A_T), radiative lifetime (τ_R) and branching ratios (β) of the various emission transitions have been computed for both Eu³⁺ and Tb³⁺:CdBiB glasses. The quenching behavior in the emission intensity with increased concentration of Eu³⁺ and Tb³⁺ was observed, which could be useful for optimizing the compositions toward practical applications.     

Intense red emission via energy transfer from (Ce3+/Eu3+):P2O5+NaF+CaF2+AlF3 glasses for warm light sources

Europium (Eu³⁺)-doped fluorophosphate (PNCA:P₂O₅+NaF + CaF₂+AlF₃) glasses with the addition of cerium (Ce³⁺) ions were fabricated by the melt-quenching technique to know their ability for the bright red (615 nm) luminescence. The emission (PL) and excitation (PLE) spectra, decay curve measurements as well as energy transfer (ET) process of Ce³⁺→ Eu³⁺ were studied in detail. An excitation spectrum related to the ⁷F₀→ ⁵D₂ level of Eu³⁺ is used to estimate the phonon energy (1121 cm^?1) of the title glass host. Under ultraviolet (UV) irradiation of 299 nm, the PL spectra of (Ce³⁺/Eu³⁺):PNCA glasses show intense red emission at 615 nm whereas the lifetime decrease with respect to increase of Eu³⁺ that could support the observed efficient ET from Ce³⁺ to Eu³⁺. The ET:Ce³⁺ →Eu³⁺ via quadrupole-quadrupole process was confirmed by Reisfeld's approximation and Dexter's ET formula. The ET efficiency (η_ET) and critical distance (R_c) were also calculated. Interestingly, the (Ce³⁺/Eu³⁺):PNCA glasses showed intense red light emission with low correlated color temperatures and the corresponding color purity reached as great as 99%, indicating its potentiality as a red component for warm light sources.     

Optical Absorption and EPR Studies on Gamma-Ray Irradiated RE<Superscript>3+</Superscript>-Doped Fluorophosphate Glasses

We have studied the effect of γ-ray irradiation on optical absorption, emission and decay characteristics of RE³⁺ (RE?=?Sm, Eu and Dy)-doped fluorophosphate glasses. Electron paramagnetic resonance (EPR) study confirms the POHC and PO₃ EC defects induced in glasses by the γ-irradiation. The presence of induced defect centers significantly affects the optical and emission properties. The optical band gap values of the studied systems increased after the γ-ray irradiation. The phonon energy and electron–phonon coupling strength of Eu³⁺-doped fluorophosphate glass were determined from the phonon sideband analysis. The emission intensity of the RE³⁺ ions increased significantly after the γ-ray irradiation. The intensity parameter, R is the ratio of the intensities of the ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁ transitions of Eu³⁺ ion and Y/B intensity parameter is the ratio of intensities of the ⁴F_9/2 → ⁶H_13∕2/⁴F_9/2 → ⁶H_15/2 transitions of Dy³⁺ ion reveal that the local environment around the RE³⁺ ion changed after the γ-ray irradiation in the present system. The lifetime of excited states of RE³⁺ ions decreased after the γ-ray irradiation due to the formation of defects induced by the γ-ray irradiation. The CIE color coordinates were determined before and after the γ-ray irradiation for the Dy³⁺-doped glass system.     

Preparation,luminescence properties and energy transfer of Ca9Y(PO4)7: Eu2+‐Tb3+ phosphors

Tb³⁺‐doped and Eu²⁺, Tb³⁺ co‐doped Ca₉Y(PO₄)₇ phosphors were synthesized by conventional solid‐state method. Additionally, the luminescence properties, decay behavior and energy transfer mechanism have already been investigated in detail. The green emission intensity of Tb³⁺ ions under NUV excitation is weak due to its spin‐forbidden f‐f transition. While Eu²⁺ can efficiently absorb NUV light and yield broad blue emission, most of which can be absorbed by Tb³⁺ ions. Thus, the emission color can be easily tuned from cyan to green through the energy transfer of Eu²⁺→Tb³⁺ in Ca₉Y(PO₄)₇:Eu²⁺,Tb³⁺ phosphor. In this work, the phenomenon of cross‐relaxation between ⁵D₃ and ⁵D₄ are also mentioned. The energy transfer is confirmed to be resulted from a quadrupole‐quadrupole mechanism.     

Investigation on Energy Transfer and Luminescent Properties of K3Gd(PO4)2:RE3+ (RE = Eu,Tb) Under UV and VUV Excitation

K₃Gd(PO₄)₂:RE³⁺ (RE = Eu, Tb) are prepared by solid‐state reaction and their photoluminescence (PL) properties are investigated under UV and VUV excitation, respectively. The obtained experimental data show that no energy transfer happens among the activator ions Tb³⁺ or Eu³⁺ under UV excitation. Under 147‐nm excitation, the strongest emission intensity of K₃Gd(PO₄)₂:RE³⁺ (RE = Eu, Tb) is obtained when the activator ions Tb³⁺ or Eu³⁺ concentration is 0.8 mol, the integrate emission intensity of K₃Gd_0.2(PO₄)₂:0.8Tb³⁺ is about 204% of commercial phosphor Zn_1.96SiO₄:0.04Mn²⁺ with chromaticity coordinates of (0.340, 0.561) and the decay time of about 5.09 ms under 147‐nm excitation. We analyze the experimental data and propose a possible energy‐transfer mechanism under 147‐nm excitation.     

Near-UV light excited Eu3+, Tb3+, Bi3+ co-doped LaPO4 phosphors: Synthesis and enhancement of red emission for WLEDs

A series of single-phase Eu³⁺, Tb³⁺, Bi³⁺ co-doped LaPO₄ phosphors were synthesized by solid-state reaction at 800 °C. Crystal structures of the phosphors were investigated by X-ray diffraction (XRD). A monoclinic phase was confirmed. The excitation (PLE) and emission (PL) spectra showed that the phosphors could emit red light centered at 591 nm under the 392 nm excitation, which is in good agreement with the emission wavelength from near-ultraviolet (n-UV) LED chip (370–410 nm). The results of PLE and PL indicated that the co-doped Tb³⁺ and Bi³⁺could enhance emission of Eu³⁺ and the fluorescent intensities of the phosphors excited at 392 nm could reach to a maximum value when the doping molar concentration of Tb³⁺ and Bi³⁺ is about 2.0% and 2.0%, respectively. The co-doping Tb³⁺ and Bi³⁺ ions can strengthen the absorption of near UV region. They can also be efficient to sensitize the emission of Eu³⁺, indicating that the energy transfer occurs from Tb³⁺ and Bi³⁺ to Eu³⁺ ions. From further investigation it can be found that co-doping Tb³⁺ and Bi³⁺ ions can also induce excitation energy reassignment between ⁵D₀–⁷F₁ and ⁵D₀–⁷F₂ in these phosphors, and result in more energy assignment to ⁵D₀–⁷F₂ emission in LaPO₄:Eu³⁺, Tb³⁺, Bi³⁺. Our research results displayed that La_0.94PO₄:Eu³⁺_0.02, Tb³⁺_0.02, Bi³⁺_0.02 could be a new one and could provide a potential red-emitting phosphor for UV-based white LED.     

Effective sensitization of Eu3+ ions on Eu3+/Nd3+ co-doped multicomponent borosilicate glasses for visible and NIR luminescence applications

Eu³⁺/Nd³⁺ co-doped multicomponent borosilicate glasses (ND1E: 10BaO +10ZnF₂+10K₂O +20SiO₂+(49-x) B₂O₃+1Nd₂O₃+xEu₂O₃) were prepared by conventional melting and rapid quench technique to evaluate the effect of Eu³⁺ ions in the Nd³⁺ doped glasses. Thermal stability, structural and spectroscopic characteristics of the ND1E glasses were investigated by using DSC, XRD, FTIR, Optical absorption, excitation and emission measurements. The Judd – Ofelt (JO) analysis is implemented to the absorption spectrum of the prepared glassy matrix in order to identify their potential applicability in lasing devices. Enhancement of ⁷F₀ → ⁵L₆ band (394 nm) with the increasing concentration of Eu³⁺ ion in the Nd³⁺ excitation spectra (λ_emi = 1060 nm) reveals the possibility of obtaining the characteristic fluorescence spectra of Nd³⁺ ion with the typical excitation wavelengths (Nd³⁺ = 584 nm and Eu³⁺ = 394 nm) of both rare earth ions and it is further verified from the emission spectrum. This interesting luminescence effect of showing excellent visible and NIR emission under 394 nm excitation mainly attributes the energy transfer mechanism between the RE³⁺ ions and the reason underlying this effect is discussed in detail with the help of partial energy level diagram. Energy transfer efficiency between the Eu³⁺ and Nd³⁺ ions were evaluated by using the radiative lifetimes of the prepared glasses. Also, a comparison of radiative properties and lasing characteristics of Eu³⁺/Nd³⁺ co-doped glasses with other Nd³⁺ glasses are reported. The emission intensities were characterized using CIE chromaticity diagram and the observed CIE coordinates shows a shift towards reddish – orange region with the increase in Eu³⁺ concentration. The quantum efficiency of the prepared glasses was determined experimentally. The obtained results suggest that the ND1E glassy system can be considered as a potential candidate for visible and NIR luminescence applications.     

Energy transfer and multicolor tunable emission in single-phase Tb3+, Eu3+ co-doped Sr3La(PO4)3 phosphors

A series of green-to-red color-tunable Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors were prepared by high temperature solid-state method. The crystal structures, photoluminescence properties, fluorescence lifetimes, and energy transfer of Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ were systematically investigated in detail. The obtained phosphors show both a green emission from Tb³⁺ and a red emission from Eu³⁺ with considerable intensity under ultraviolet (UV) excitation (~377 nm). The emission colors of the phosphors can be tuned from green (0.304, 0.589) through yellow (0.401, 0.505) and eventually to red (0.557, 0.392) due to efficient Tb³⁺-Eu³⁺ energy transfer (ET). The Tb³⁺→Eu³⁺ energy transfer process was demonstrated to be quadrupole-quadrupole mechanism by Inokuti-Hirayama model, with maximum ET efficiency of 86.3%. The results indicate that the Sr₃La(PO₄)₃:Tb³⁺, Eu³⁺ phosphors might find potential applications in the field of lighting and displays.     

A single‐phase full‐color emitting phosphor Na3Sc2(PO4)3:Eu2+/Tb3+/Mn2+ with near‐zero thermal quenching and high quantum yield for near‐UV converted warm w‐LEDs

A single‐phase full‐color emitting phosphor Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ has been synthesized by high‐temperature solid‐state method. The crystal structure is measured by X‐ray diffraction. The emission can be tuned from blue to green/red/white through reasonable adjustment of doping ratio among Eu²⁺/Tb³⁺/Mn²⁺ ions. The photoluminescence, energy‐transfer efficiency and concentration quenching mechanisms in Eu²⁺‐Tb³⁺/Eu²⁺‐Mn²⁺ co‐doped samples were studied in detail. All as‐obtained samples show high quantum yield and robust resistance to thermal quenching at evaluated temperature from 30 to 200°C. Notably, the wide‐gamut emission covering the full visible range of Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ gives an outstanding thermal quenching behavior near‐zero thermal quenching at 150°C/less than 20% emission intensity loss at 200°C, and high quantum yield‐66.0% at 150°C/56.9% at 200°C. Moreover, the chromaticity coordinates of Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ keep stable through the whole evaluated temperature range. Finally, near‐UV w‐LED devices were fabricated, the white LED device (CCT = 4740.4 K, Ra = 80.9) indicates that Na₃Sc₂(PO₄)₃:Eu²⁺/Tb³⁺/Mn²⁺ may be a promising candidate for phosphor‐converted near‐UV w‐LEDs.     

Effect of codoping Ce3+ on the luminescence properties of Sr9Mg1.5(PO4)7:Eu2+ orange–yellow phosphor

Sr₉Mg_1.5(PO₄)₇:Eu²⁺ has recently been reported as a promising blue light-excited orange–yellow phosphor that can be used in white LED device. Here, Ce³⁺-codoping is found to be an effective strategy to improve the luminescence performance of Sr₉Mg_1.5(PO₄)₇:Eu²⁺ phosphor. The coexistence of Eu²⁺ and Eu³⁺ ions has been verified via photoluminescence spectral analysis. The reduction of Eu³⁺ to Eu²⁺ in Sr₉Mg_1.5(PO₄)₇ lattice cannot be completed in a reducing atmosphere, but can be promoted through codoping with Ce³⁺ ions to a great extent, which finally increase the effective concentration of Eu²⁺ in the crystal lattice. The Eu³⁺−Eu²⁺ reduction mechanism is analyzed using a charge compensation model. This work not only achieves enhanced luminescence of the Sr₉Mg_1.5(PO₄)₇:Eu²⁺ phosphor by codoping with Ce³⁺ ions, but also provides new insights into the design of Ce³⁺/Eu²⁺ codoped luminescent materials.     

Luminescence characteristics and energy transfer of Eu2+/Tb3+ doped single phase multi-color phosphor

The investigation on single phase multi-color phosphors is highly meaningful for near-ultraviolet chip based white light emitting diodes. In this work, a series of Eu²⁺ and Tb³⁺ singly doped and Eu²⁺/Tb³⁺ codoped Sr₅(PO₄)₃Cl phosphors were synthesized via a high-temperature solid state reaction method. The luminescence spectra and decay curves of Eu²⁺ and Tb³⁺ singly doped samples were discussed, the optimal doping concentrations were determined. Thanks to the spectra overlap between Eu²⁺ and Tb³⁺, nonradiative energy transfer from Eu²⁺ to Tb³⁺ was investigated. It is found electric dipole-dipole interaction played the main role for the energy transfer in codoped samples, the highest energy transfer efficiency was calculated to be 60.98%. Tunable emissions are observed for codoped samples by adjusting doping concentration. The thermal quenching properties were discussed and the activation energy (ΔE) was estimated in the present work.     

Novel Broadband Excited and Linear Red‐Emitting Ba2Y(BO3)2Cl: Ce3+, Tb3+, Eu3+ Phosphor: Luminescence and Energy Transfer

A series of Ce³⁺, Tb³⁺, Eu³⁺ tri‐doped Ba₂Y(BO₃)₂Cl red‐emitting phosphor have been synthesized by solid‐state method. The Ce³⁺→Tb³⁺→Eu³⁺ energy‐transfer scheme has been proposed to realize the sensitization of Eu³⁺ ion emission by Ce³⁺ ions. Following this energy‐transfer model, near‐UV convertible Eu³⁺‐activated red phosphors have been obtained in Ba₂Y(BO₃)₂Cl: Ce³⁺, Tb³⁺, Eu³⁺ phosphors. Energy transfers from Ce³⁺ to Tb³⁺, and Tb³⁺ to Eu³⁺, as well as corresponding energy‐transfer efficiencies are investigated. The combination of narrow‐line red emission and near‐UV broadband excitation makes Ba₂Y(BO₃)₂Cl: Ce³⁺, Tb³⁺, Eu³⁺ as a novel and efficient red phosphor for NUV LED applications.     

Combustion synthesis of LaSi3N5:Eu2+ phosphor powders

LaSi₃N₅:Eu²⁺ phosphor powders were prepared by a highly efficient combustion synthesis method. It was found that the compositions of the raw powder mixtures had great influences on the phase compositions and particle morphologies of the synthesized powders. By selecting appropriate starting compositions and combustion parameters, single phase LaSi₃N₅:Eu²⁺ phosphors could be synthesized. When excited by a UV light, the LaSi₃N₅:Eu²⁺ phosphors emitted green light. The wavelength and intensity of the emission spectra were affected by the amount of Eu²⁺ dopant. With increasing amount of Eu²⁺ dopant, concentration quenching could occur and emission spectra shifted to longer wavelengths.     

Effect of A+ (A = Li,Na and K) co-doping on enhancing the luminescence of Ca5(PO4)2SiO4:Eu3+ red-emitting phosphors as charge compensator

A series of Ca_5-x(PO₄)₂SiO₄:xEu³⁺ red-emitting phosphors were synthesized through solid-state reaction, and alkali metal ions A⁺ (A = Li, Na and K) were co-doped in Ca₅(PO₄)₂SiO₄:Eu³⁺ to improve its luminescence property. The impacts of synthesis temperature, luminescence center Eu³⁺ concentration and charge compensator A⁺ on the structure and luminescence property of samples were studied in detail. X-ray diffraction results indicated that prepared Ca₅(PO₄)₂SiO₄:Eu³⁺, A⁺ had a standard Ca₅(PO₄)₂SiO₄ structure with space group P6₃/m. Under the excitation of 392 nm, Ca₅(PO₄)₂SiO₄:Eu³⁺ phosphors showed a red emission consisting of several emission peaks at 593 nm, 616 nm and 656 nm, relevant to ⁵D₀→⁷F₁, ⁵D₀→⁷F₂ and ⁵D₀→⁷F₄ electron transitions of Eu³⁺ ions, respectively. Luminescence intensity and lifetime of Ca₅(PO₄)₂SiO₄:Eu³⁺ can be significantly enhanced through co-doping alkali metal ion A⁺, which play an important role as charge compensator. The results suggest that Ca₅(PO₄)₂SiO₄:Eu³⁺, A⁺ red phosphors with excellent luminescence property are expectantly served as red component for white light-emitting diodes excited by near-ultraviolet.