Synthesis and optical characterization of Eu2+,Tb3+-codoped Sr3Y(PO4)3 green phosphors

A series of Eu~(2+),Tb~(3+)-codoped Sr_3 Y(PO_4)_3(SYP) green phosphors were synthesized by hightemperature solid-state reaction. Several techniques, such as X-ray diffraction, UV-vis spectrum,and photoluminescence spectrum, were used to investigate the obtained phosphors. The present study investigates in detail photoluminescence excitation and emission properties, energy transfer between the two dopants, and effects of doping ions on optical band gap. SYP:0.05 Eu2+ phosphor shows an intense and broad excitation band ranging from 220 to 400 nm and exhibits a bright green emission band with CIE chromaticity coordinates(0.189, 0.359) under 350 nm excitation. Green emission of SYP:0.03 Tb3+ is intensified by codoping with Eu~(2+), and energy transfer mechanism between them is demonstrated to be a dipole-dipole interaction. Upon 350 nm excitation, SYP:Eu~(2+),Tb~(3+) phosphors exhibits two dominating bands peaking at 466 and 545 nm, which are assigned to 4 f~65 d~1→4 f~7 transition of Eu~(2+) ions and ~5 D_4→~7 F_5 transition of Tb~(3+) ions, respectively. Optimal doping concentrations of Eu~(2+) and Tb~(3+) in the SYP host are 5 mol% and 15 mol%, respectively. Results indicate that SYP:Eu~(2+),Tb~(3+) phosphors are potentially used as green-emitting phosphors for white light-emitting diodes.     

Color-tunable Ca10Na(PO4)7:Ce3+/Tb3+/Mn2+ phosphor via energy transfer

A series of Ca_(10)Na(PO_4)_7:Ce~(3+)/Tb~(3+)/Mn~(2+)(CNPO:Ce~(3+)/Tb~(3+)/Mn~(2+)) phosphors with high brightness were synthesized by high-temperature solid-state method. X-ray diffraction(XRD), scanning electron microscopy(SEM), diffuse reflectance spectra(DRS), photo luminescence(PL) spectra, luminescence decay curves and thermally stability were performed to characterize the as-prepared samples. For Ce~(3+)-doped samples, an intense and broad band emission is present under 265 nm excitation. When Ce~(3+) and Tb~(3+)are codoped, energy transfer(ET) process from Ce3+ to Tb3+ is demonstrated with electric dipole-dipole interaction. The internal and external quantum efficiencies(QEs) of CNPO:0.15 Ce~(3+), 0.04 Tb~(3+), 0.005 Mn~(2+)are measured to 76.79% and 54.11% under 265 nm excitation and temperature-dependent PL intensity can remain 51.78% at 150 ℃ of its initial intensity at 25 ℃. It is indicated that single-phased white lightemitting CNPO:Ce~(3+)/Tb~(3+)/Mn~(2+) phosphor can serve as a promising phosphor for illumination devices.     

White-light emitting single-phase phosphor La3Si6N11:Dy3+,Tb3+: Color tunable emission,thermal stability and energy transfer process

A novel white-light emitting single-phase phosphor La₃Si₆N₁₁:Dy³⁺, exhibiting two emission peaks centering at 475 and 575 nm, was prepared via conventional solid-state reactions. The structure and morphology of La₃Si₆N₁₁:Dy³⁺/Tb³⁺ were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The emission colors can be tuned from white to yellow-green through increasing the Tb³⁺ concentration in La₃Si₆N₁₁:Dy³⁺,Tb³⁺. The mechanism of energy transfer (ET) from Dy³⁺ to Tb³⁺ is confirmed according to the excitation, emission spectra and decay lifetimes curve. The temperature-dependent luminescence measurements of La_2.83Si₆N₁₁:0.1Dy³⁺,0.07Tb³⁺ were also performed, and a good thermal stability is shown, suggesting superior properties for the application as white light-emitting diodes (w-LEDs) phosphor.     

Single-phase white-emitting and tunable color phosphor Na3Sc2(PO4)3:Eu2+,Dy3+: Synthesis,luminescence and energy transfer

A series of Eu²⁺/Dy³⁺ single doped and co-doped Na₃Sc₂(PO₄)₃ phosphors were synthesized by the high-temperature solid-state method, and their phase, morphology, and luminescence properties were characterized. Under the excitation of 370 nm, the Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor can emit white light whose spectrum is composed of a broad emission band centered at 460 nm and the other three peaks at 483, 577, and 672 nm, respectively. There is energy transfer from Eu²⁺ to Dy³⁺ ion in Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor due to the good overlap between the emission spectrum of Na₃Sc₂(PO₄)₃:Eu²⁺ and the excitation spectrum of Na₃Sc₂(PO₄)₃:Dy³⁺, which is further confirmed by the fluorescence lifetime decrease of Eu²⁺ ion with the increase of Dy³⁺ concentration. The process of energy transfer is via dipole–quadruple interaction which is confirmed by applying Dexter's theory. By increasing the Dy³⁺ concentration, the color coordinates of the Na₃Sc₂(PO₄)₃:0.01Eu²⁺,xDy³⁺ phosphors can be adjusted from blue to white, and then to yellow. The optimized concentration of Dy³⁺ ions is 4.0 mol%, beyond which the concentration quenching will take place. The Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor shows fairly good resistance to thermal quenching behavior, of which the emission intensity at 423 K can maintain 90.3% of the initial value (298 K). These results suggest that the Na₃Sc₂(PO₄)₃:0.01Eu²⁺,xDy³⁺ phosphors have potential applications as the color-tunable or a single-phase white emitting phosphor in white LEDs.     

Tunable emission,energy transfer and thermal stability of Ce3+, Tb3+ co-doped Na2BaCa(PO4)2 phosphors

A series of single Ce³⁺ doped and Ce³⁺ and Tb³⁺ co-doped Na₂BaCa(PO₄)₂ (NBCP) phosphors was synthesized by conventional solid-stated reaction method. The crystal structure, luminescence properties, thermal stability and energy transfer were carefully investigated. Ce³⁺ is inferred to substitute the Ba²⁺ site in NBCP lattice. The color-tunable emission from blue to green is observed by adjusting Tb³⁺ concentration among NBCP:0.03Ce³⁺,yTb³⁺ phosphors. The energy transfer behavior from Ce³⁺ to Tb³⁺ ions is both illustrated by co-doped PL spectra and decay curves. The energy transfer efficiency is as high as 91.5%. The mechanism of energy transfer is resonance type of dipole-dipole transition. In this work, the optimal phosphor exhibits the excellent thermal stability which keeps at 94.9% of that initial value at room temperature when temperature reaches to 150 °C. The Ce³⁺ and Tb³⁺ co-doped NBCP phosphor is a promising candidate for the application in the general lighting and display fields.     

Site occupation and energy transfer in full color emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+

White light-emitting diodes (WLEDs) fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting. The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor. Here, we report a high quality white light-emitting phosphor Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ with spectral distribution covering whole visible region. Blue light emission originates from Ce³⁺ ions occupying preferentially Ba²⁺ site by controlling synthesis conditions. Green and red lights are obtained from Eu²⁺ occupying Ba²⁺ (and Ca²⁺) site and Mn²⁺ occupying Ca²⁺ site, respectively. In this triple-doped phosphor, strong red emission with a low concentration of Mn²⁺ is realized by the efficient energy transfer from Ce³⁺ and Eu²⁺ to Mn²⁺. Furthermore, high quality white light is accomplished by properly tuning the relative doping amount of Ce³⁺(K⁺)/Eu²⁺/Mn²⁺ based on efficient simultaneous energy transfer. The results indicate that Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ is a promising white light-emitting phosphor in WLEDs application.     

Tunable emission properties of tri-doped Ca_9LiY_(2/3)(PO_4)_7:Ce~(3+),Tb~(3+),Mn~(2+) phosphors with warm white emitting based on energy transfer

Tri-doped Ca_9 LiY_(2/3)(PO_4)_7:Ce~(3+),Tb~(3+),Mn~(2+)phosphors were prepared by a high-temperature solid state method.Under UV light excitation,Ca_9 LiY_(2/3)(PO_4)_7:Ce~(3+)samples exhibit a broad band ranging from 320 to 500 nm.At 77 K,the emission spectra of Ca_9 LiY_(2/3)(PO_4)7:Ce~(3+)samples present two obvious emission peaks,indicating that Ce~(3+)ions occupy two different kinds of lattice sites(Ca(1/2) and Ca(3)),As a good sensitizer for Tb~(3+),Ce~(3+)ions in Ca_9 LiY_(2/3)(PO_4)_7 lattice can effectively transfer part of energy to Tb~(3+),and the energy trans fer mechanism is determined to be dipole-dipole interaction.Consequently,the emitting color for Ce~(3+) and Tb~(3+) co-doped Ca_9 LiY_(2/3)(PO_4)_7 samples can be tuned from bluish violet to green.In order to further enlarge the emission gamut,Mn~(2+)ions as red emission components were added,forming tri-doped single-phase Ca_9 LiY_(2/3)(PO_4)_7:Ce~(3+),Tb~(3+),Mn~(2+)phosphors.The Ca_9 LiY_(2/3)(PO_4)_7:Ce~(3+),Tb~(3+),Mn~(2+)phosphors exhibit tunable emission properties through controlling the relative doping concentration of Ce~(3+),Tb~(3+)and Mn~(2+).Especially,Ca_9 LiY_(2/3)(PO_4)_7:0.09 Ce~(3+),0.12 Tb~(3+),0.30 Mn~(2+)can emit warm white light.The sample shows good thermal stability.At 150℃,the emission intensity for Ce~(3+)(360 nm),Tb~(3+)(545 nm) and Mn~(2+)(655 nm) decreases to 63%,69%,and 72% of its initial intensity,respectively.Moreover,the sample obtains good stability after 10 cycles between room temperature and150℃.     

Structure and luminescence properties of color-tunable phosphor Sr2La3(SiO4)3F:Tb3+,Sm3+

A series of single-phase and color-tunable phosphors Sr₂La₃(SiO₄)₃F:0.15Tb³⁺,xSm³⁺(SLSOF:0.15Tb³⁺,xSm³⁺) was prepared using solid-state route.The X-ray diffraction(XRD) was used to characterize the phase of the as-prepared samples.The synthesized phosphors have apatite-type structure without other impurities.Sm³⁺ and Tb³⁺ ions substitute La³⁺ into the lattice and form a single...     

Luminescence of halophosphate solid-solution Ca5(PO4)3(F0.8Cl0.2):Eu2+,Mn2+ for WLED

Solid-solution based luminescent materials have been widely explored due to their tunable optical properties in recent years. In this work, instead of more common cation-substitution approach, we investigated the luminescence properties of Eu~(2+) and Mn~(2+) co-doped halophosphate solid solution Ca_5(PO_4)_3(F_(0.8)Cl_(0.2)) via anion substitution synthesized by high temperature solid state reaction method.The formation of the solid solution was confirmed by X-ray diffraction(XRD) characterization, which indicates that the introduction of certain proportion of Cl~-will not make significant change on the Ca_5(PO_4)_3F lattice. We also studied the energy transfer from Eu~(2+) to Mn~(2+) in the host so as to obtain white light emission via adjusting the doping concentrations of Eu~(2+) and Mn~(2+). The white light emission was achieved through combination of Eu~(2+) blue emission and Mn~(2+) red-orange emission with appropriate proportions. The results suggest that Ca_5(PO_4)_3(F_(0.8)Cl_(0.2)):0.01Eu~(2+),0.18 Mn~(2+) could be a potential WLED phosphor working under ultraviolet excitation.     

Upconversion multicolor tuning of NaY(WO4)2:Tb3+ with Eu3+ doping

A series of Tb~(3+) and Eu~(3+) co-doped NaY(WO_4)_2 phosphors were synthesized by hydrothermal reactions.The crystal structure,morphology,upconversion luminescent properties,the energy transfer from Tb~(3+) to Eu~(3+)ions and the ~5 D_4→ ~7 F_5 transition of the Tb~(3+) ion in NaY(WO_4)_2:Tb~(3+),Eu~(3+) phosphors were investigated in details.The results indicate that all the synthesized samples are of pure tetragonal phase NaY(WO_4)2.Furthermore,the micrometer-sized needle spheres and excellent dispersion of the particles are obtained by adding polyethylene glycol(PEG-2000) as the surfactant.Phosphors of NaY(WO_4)_2:Tb~(3+),Eu~(3+) exhibit the492 nm blue emission peak,546 nm green emission peak,595 nm orange emission peak and 616 nm red emission peak under 790 nm excitation.The energy transfer from Tb~(3+) to Eu~(3+) is a resonant transfer,in which electric dipole-dipole interaction plays a leading role.By adjusting the doping concentration of Eu~(3+) in NaY(WO_4)_2: 1.0 mol%Tb~(3+),xmol%Eu~(3+) phosphors,the emitting color of UC phosphors can be tuned from green to red.     

Luminescent and thermometric properties of dual emitting Eu~(2+)/Sm~(3+) co-doped Sr_4La(PO_4)_3O phosphor based on energy transfer

Eu²⁺/Sm³⁺co-doped dual-emitting Sr₄La(PO₄)₃O phosphors were synthesized through a convenient high temperature solid state reaction in reductive atmosphere.The structure,luminescence,energy transfer and temperature-dependent luminescence properties of Eu²⁺/Sm³⁺co-doped Sr₄La(PO₄)₃O phosphors were researched and analyzed in detail.The blue emission of Eu²⁺and the red emission of Sm³⁺can work together as FIR signals.Based on the different response characteristics of these two ion emissions to temperature,Sr₄La(PO₄)₃O:Eu²⁺/Sm^(³⁺)phosphor achieves the relative sensitivity of0.48384%/K and a wide range of temperature measurements from room temperature to 573 K.The results reveal that the Sr₄La(PO₄)₃O:Eu²⁺/Sm³⁺phosphor has application prospect in the field of high temperature optical thermometry.The energy transfer mechanism is proved to be the dipole-dipole interaction between Eu²⁺and Sm³⁺ions.     

A NIR to NIR rechargeable long persistent luminescence phosphor Ca2Ga2GeO7:Yb3+,Tb3+

Near infrared to near infrared (NIR–NIR) photo-stimulated persistent luminescence (PSPL) has shown excellent potential in high-resolution bioimaging for deep tissues. However, the PSPL in NIR-Ⅱ region (900–1700 nm) is still lacking. In this work, Ca₂Ga₂GeO₇:Yb³⁺,Tb³⁺ (CGGYT) phosphor with unique low-dimensional crystal structure was synthesized by high-temperature solid–state reaction. Thanks to the carriers transferring from deep traps to shallow ones induced by low energy light, the 978 nm PSPL originating from ²F_5/2 to ²F_7/2 transition of Yb³⁺ induced by multimode stimulating (980 nm or WLED) is successfully realized after pre-excited by UV lamp. The NIR PSPL of the specimen can be repeatedly stimulated after placed in dark for 12 h. Moreover, the results indicate that codoping with Tb³⁺ can significantly enhance the NIR-II PSPL owing to the quantum cutting persistent energy transfer (QC PET) from Tb³⁺ to Yb³⁺. Our study points to a new direction for the future development of multimode PSPL materials for bioimaging or multimode optical storage applications.     

Eu3+-doped BaLiZn3(BO3)3: A novel red-emitting phosphor for blue chips excited white LEDs

A series of novel red-emitting BaLiZn₃(BO₃)₃:Eu³⁺ phosphors were synthesized through the high temperature solid state reaction method. The phase composition, crystal structure, morphology and photoluminescence property of the BaLiZn₃(BO₃)₃:Eu³⁺ samples were systematically investigated. The phosphor can be efficiently excited by the near ultraviolet light (NUV) of 396 nm and blue light of 466 nm, and give out red light emission at 618 nm corresponding to the electric dipole transition (⁵D₀→⁷F₂). The optimal doping concentration of Eu³⁺ ions in BaLiZn₃(BO₃)₃ is determined to be about 3 mol%, and the concentration-quenching phenomenon arise from the electric dipole–dipole interaction. The temperature dependent luminescence behavior of BaLiZn₃(BO₃)₃:0.03Eu³⁺ phosphor exhibits its good thermal stability, and the activation energy for thermal quenching characteristics is calculated to be 0.1844 eV. The decay lifetime of the BaLiZn₃(BO₃)₃:0.03Eu³⁺ is measured to be 1.88 ms. These results suggest that the BaLiZn₃(BO₃)₃:Eu³⁺ phosphors have the potential application as a red component in white light emitting diodes (WLEDs) with NUV or blue chips.     

Energy transfer and luminescent properties of Tb3+ and Tb3+, Yb3+ doped CNGG phosphors

In this work,calcium niobium gallium garnet(Ca₃ Nb_1.6875Ga_3.1875O₁₂-CNGG) ceramic samples singledoped with Tb³⁺ and co-doped with Tb³⁺ and Yb³⁺ ions were sintered by the solid-state reaction method.The structural characterization of the samples was carried out by X-ray diffraction measurements.The optimal concentration of Tb³⁺ ions corresponding to the maximum luminescence in the green spectral range in CNGG:...     

Synthesis and photoluminescence properties of Er3+ and Dy3+ doped Na2NbAlO5 phosphors

A series of Ln³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) ions doped Na₂NbAlO₅ (NNAO) phosphors were synthesized by solid-state method. The Er³⁺ and Dy³⁺ ions doped phosphors were characterized by XRD, photoluminescence (PL) and decay profiles. The Ln³⁺-doped samples are consistent with the pure NNAO phase which is analyzed by the X-ray diffraction result. The PL graphs show that the intensity of luminescence increases with the increasing doping concentrations up to their critical certain values and then decreases at higher concentrations due to the concentration quenching effect of Er³⁺/Dy³⁺ ions. The energy level diagrams containing the positions of 4f and 5d energy levels of Er³⁺ and Dy³⁺ ions have been established and studied. In addition, under the ultraviolet light, the prepared NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors show the characteristic green (Er³⁺), cyan (Dy³⁺) emission, respectively. Under the excitation of 365 nm, the quantum efficiencies of NNAO:0.01Er³⁺ and NNAO:0.03Dy³⁺ phosphors are measured to be 61.7% and 72.2%, respectively. The obtained results indicate that the new NNAO:xLn³⁺ (Ln³⁺ = Er³⁺/Dy³⁺) phosphors are promising applications in white-light emitting diodes field.     

Eu2+-doped Sr5(PO4)3Br blue-emitting phosphor with high color purity for near-UV-pumped white light-emitting diodes

Eu²⁺-doped bromophosphateapatite Sr₅(PO₄)₃Br phosphors were synthesized by the conventional high-temperature solid-state reaction. The crystal structure and luminescence properties of the phosphors, as well as their thermal stability and CIE chromaticity coordinates were systematically investigated. Photoluminescence spectra of Sr₅(PO₄)₃Br:Eu²⁺ exhibit a single blue emission at 450 nm under the excitation of 345 nm, which is ascribed to the 4f–5d transition of Eu²⁺. The phosphor shows very good thermal stability. The CIE color coordinates are very close to those of BaMgAl₁₀O₁₇:Eu²⁺ (BAM). All the properties indicate that the blue-emitting Sr₅(PO₄)₃Br:Eu²⁺ phosphor has potential application in white LEDs.     

Cooperative energy transfer in Eu3+,Yb3+ codoped Y2O3 phosphor

Under 980 nm laser excitation,red emission(5D0-7FJ(J=0,1,2)) of Eu3+ was observed in cubic Y2O3 codoped with Eu3+ and Yb3+.The dependence of the upconverted emission on doping concentration and laser power was studied.Yb3+ emission around 1000 nm(2F5/2-2F7/2) was reported upon excitation of Eu3+ ions.The decay curves of 5DJ(J=0,2) emission of Eu3+ under excitation of 266 nm pulse laser were examined to investigate the Eu3+→Yb3+ energy transfer process.Cooperative energy transfer process was discussed as the possible mechanism for the visible up-conversion luminescence of Eu3+ and near-infrared down-conversion emission of Yb3+.     

Red-emitting CaWO4:Eu3+,Tm3+ phosphor for solid-state lighting: Luminescent properties and morphology evolution

CaWO₄:xEu³⁺,yTm³⁺crystals were obtained by facile synthesis at low temperature by the microwaveassisted hydrothermal method(MAH).The phase formation,morphology,luminescent properties and ene rgy transfer were investigated.The X-ray diffraction(XRD)re sults show the formation of a scheelitelike tetragonal structure without the presence of secondary phases.The growth mechanism of hierarchical micro structures based on self-assembly and Ostwald-ripening processes was evaluated,obtaining different types of morphologies.The luminescence spectra of CaWO₄:Eu³⁺,Tm³⁺at 325 nm excitation show the predominance of red emission at the 5 D0→7 F2(Eu³⁺)transition at 624 nm.This feature signals dominant behavior of the electric dipole type.The presence of Tm³⁺is notably evident in the absorption spectra by the related excitation transitions:3 H6→1 G4,3 H6→3 F3 and 3 H6→3 H4.Color parameters are discussed to characterize CaWO₄:Eu³⁺,Tm³⁺emission.The study of the emission spectrum as a function of the concentration of Eu³⁺(x mol%)and Tm³⁺(y mol%)indicates that the CaWO₄:Eu³⁺,Tm³⁺phosphors show stronger red emission intensity and exhibit the CIE value of x=0.63 and y=0.35.The photoluminescence results show 97%high color purity for CaWO₄:4 mol%Eu³⁺,a high CRI(92%)and a low CCT of 1085 K.These results demonstrate that the CaWO₄:Eu³⁺,Tm³⁺red phosphors are promising as color converters for application in white light-emitting diodes and display devices.     

Investigation on luminescence of red-emitting Mg3Ca3(PO4)4:Ce3+,Mn2+ phosphors

To realize red emission, the Ce3+-Mn2+ activated Mg3Ca3(PO4)4 phosphors were synthesized by solid-state reaction. The phase and luminescence properties of the as-prepared samples were characterized by ...     

Effect of Eu3+ doping on luminescence properties of a KAlSiO4:Sm3+ phosphor

This study presents the photoluminescence characteristic analysis of a series of red phosphors of KAlSiO₄:1.5 mol%Sm³⁺,x mol%Eu³⁺ (x = 2, 3, 4, 5, 6, 7) prepared via high-temperature solid-phase reaction. The results show that the X-ray diffraction (XRD) refinement results are reliable. The unit cell parameters and volume gradually decrease as the Eu³⁺ concentration increases, resulting in a grain size reduction of 10.22%. When x = 6, the emission peaks of Sm³⁺ at 564, 601, and 651 nm disappear completely, and the corresponding full width at half maximum becomes 0. At 610 nm, the emission peak intensity of Eu³⁺ is increased by a factor of 4.8. The resonant non-radiative energy transfer effect is greater than the co-excitation effect. A maximum energy transfer efficiency of 97.8% is achieved. The integral area at 610 nm is as high as 85%. The color purity of the phosphor is as high as 92.97%, and the internal quantum yield gradually changes from 32% to 51%. Ultimately, these results confirm that the silicate phosphor is suitable for the red component in the three primary color phosphors of white light-emitting diodes.