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.     

Energy transfer,superior thermal stability and multi-color emitting properties of langbeinite-type solid-solution phosphor K_2Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3

Langbeinite type compounds are a large kind of oxometallate with good flexibility structure.Herein,we synthesized a new langbeinite type compound K_2 Dy_(1.5)Ta_(0.5)(PO_4)_3,in which the Dy~(3+) and Ta~(5+) were blended to occupy the same crystallographic sites.Simultaneously,solid solutions of K_2 Dy_(1.5)_(-x)Eu_xTa_(0.5)(PO_4)_3(x=0-1.5) were prepared and their photoluminescence properties were investigated.Due to energy transfer from Dy~(3+) to Eu~(3+),both Dy~(3+) and Eu~(3+) characteristic emissions are observed under 393 nm light excitation.The emitting color of K_2 Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3 turns from green through yellow to red by simply adjusting the Eu~(3+) concentration from 0 to 0.4.Moreover,K_2 Dy_(1.48)Eu_(0.02)Ta_(0.5)(PO_4)_3 phosphor possesses excellent fluorescence thermal stability and exhibits zero thermal quenching at 150 ℃.These results manifest that K_2 Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3 solutions are promising multi-color emitting phosphors candidate for near-UV LED.     

Multi-site occupancies and luminescence properties of cyan-emitting Ca9-xNaGd2/3(PO4)7:Eu2+phosphors for white light-emitting diodes

Cyan-emitting Ca₉NaGd_2/3(PO₄)₇:Eu²⁺phosphors were synthesized via high temperature solid-state route.X-ray powder diffraction(XRD)and scanning electron microscopy(SEM)were used to verify the phase and morphology of the Ca₉NaGd_2/3(PO₄)₇:Eu²⁺(CNGP:Eu²⁺)phosphors.The as-obtained phosphor exhibits a broad excitation band of 250-420 nm,which is near the ultraviolet region.An intense asymmetric cyan emission at 496 nm corresponds to the 5 d-4 f transition of Eu²⁺.The multiplesite luminescent properties of Eu²⁺ions in CNGP benefit from versatile structure ofβ-Ca3(PO4)2 compounds.The effective energy transfer distance is 5.46 nm(through the spectral overlap calculation),validating that the resonant energy migration type is via dipole-dipole interaction mechanism.Compared to the initial one at room temperature,the luminescent intensity of CNGP:Eu²⁺phosphor can maintain 77%as it is heated up to 420 K.A white light-emitting diode(WLED)with excellent luminesce nt properties was successfully fabricated.Moreover,the CIE chromaticity coordinates of fabricated WLED driven by changing current just change slightly.     

Eu2＋ and Dy3＋ codoped （Ca,Sr）7（SiO3）6Cl2 highly efficient yellow phosphor

Eu2+ and Dy3+ codoped(Ca,Sr)7(SiO3)6Cl2 yellow phosphors were successfully synthesized by self-flux method. The structure, morphology and photoluminescence properties were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and photoluminescence spectra. The as-prepared phosphor showed a broad emission spectrum centered at 550 nm for Eu2+single-doped phosphor, while located at 548–544 nm for the Eu2+, Dy3+ codoped samples under excitation at 380 nm light. The emission intensity was greatly improved when Dy3+ was doped into the(Ca,Sr)7(SiO3)6Cl2:Eu2+ system. The composition-optimized sample with 3 mol.% of Dy3+ and constant 10 mol.% of Eu2+ exhibited a 220% PL enhancement compared to the phosphor with 10 mol.% Eu2+ single-doped. Meanwhile, it was found that the quantum efficiency of phosphor namely(Ca,Sr)7(SiO3)6Cl2:3 mol.% Dy3+, 10 mol.% Eu2+ could get up to 24.6%. The synthesized yellow-emitting(Ca,Sr)7(SiO3)6Cl2:Dy3+,Eu2+ is a promising candidate as high-efficiency yellow phosphor for NUV-excited white LEDs.     

A single-phase full-color phosphor Sr2Ca2La(PO4)3O:Eu2+,Tb3+,Mn2+: Photoluminescence and energy transfer

A single-phase full-color emitting phosphor Sr₂Ca₂La(PO₄)₃O:Eu²⁺,Tb³⁺,Mn²⁺ was synthesized by the high temperature solid-state method. The phase formation, luminescence properties, thermal stability, and energy transfer from Eu²⁺ to Tb³⁺ and Eu²⁺ to Mn²⁺ in Sr₂Ca₂La(PO₄)₃O were investigated in details. Tunable emission color from blue to blueish green or orange can be observed under 365 nm near-ultraviolet excitation based on the energy transfer from Eu²⁺ to Tb³⁺ or Mn²⁺ ions by varying the ratio of Eu²⁺/Tb³⁺ or Eu²⁺/Mn²⁺ ions. White light was obtained with chromaticity coordinates of (0.3558, 0.3500) in the Sr₂Ca₂La(PO₄)₃O:0.04Eu²⁺,0.08Tb³⁺,0.40Mn²⁺ phosphor, suggesting their potential applications in white light emitting diodes.     

Synthesis,structure and optical properties of novel thermally robust Dy~(3+)-doped Ca_9Sc(PO_4)_7 phosphors for NUV-excited white LEDs

The powder samples of Ca₉Sc(PO₄)₇:xDy^{^(3+})white emitting phosphors were prepared via a solid state reaction technique.The Ca₉Sc(PO₄)₇:Dy³⁺samples were researched by using the GSAS Rietveld refinement and X-ray diffraction(XRD) methods,and SEM images and elemental maps were recorded.Under 350 nm excitatio n,the emission spectra of Ca₉Sc(PO₄)₇:xDy³⁺samples have two obvious peaks and one weak peak at 484,572 and660 nm,corresponding to the characteristic electron transitions of(⁴F_9/2→ ⁶H_15/2,blue),(⁴F_9/2→ ⁶H_13/2,yellow) and(⁴F_9/2→ 6 H11/2,red),respectively.The concentration quenching effect,decay lifetime and thermal quenching of the as-synthesized Ca₉Sc(PO₄)₇:Dy³⁺samples were researched systematically.The Ca₉Sc(PO₄)₇:0.02 Dy³⁺phosphor possesses a good thermal stability,of which the emission intensity at 423 K can maintain 79% of the initial value(273 K).In addition,through the study of the chro maticity coordinates of the Ca₉Sc(PO₄)₇:0.02 Dy³⁺phosphor,it is found that it is located in the white region,and the Commission Internationalede L’Eclairage(CIE) chromaticity coordinates are(0.339,0.389),The above results show that Ca₉Sc(PO₄)₇:xDy³⁺phosphors can be excellent candidate material for applications in NUV-excited white LEDs.     

Synthesis and luminescence properties of SrAleO4：Eue＋,Dy3＋ hollow microspheres via a solvothermal co-precipitation method

SrAl2O4:Eu2+,Dy3+ hollow microspheres were successfully prepared through a facile and mild solvothermal co-precipitation combining with a postcalcining process.The structure and particle morphology were investigated by X-ray diffraction(XRD),scanning and transmission electron microscopy(SEM and TEM)pictures,respectively.The mechanism for the formation of spherical SrAl2O4:Eu2+,Dy3+ phosphor was preliminary presented.After being irradiated with ultraviolet(UV)light,the spherical phosphor emitted long-lasting green phosphorescence.Both the photoluminescence(PL)spectra and luminance decay,compared with that of commercial bulky powders,revealed that the phosphors had efficient luminescent and long lasting properties.It was considered that the SrAl2O4:Eu2+,Dy3+ hollow microspheres had promising long-lasting phosphorescence with potential scale-dependent applications in photonic devices.     

Intense blue-emitting Ca2PO4Cl:Eu2+ phosphor for near-ultraviolet converting white light-emitting diodes

A blue phosphor Ca₂PO₄Cl:Eu²⁺ (CAP:Eu²⁺) was synthesized by solid state reaction. The Ca₂PO₄Cl:Eu²⁺ exhibited high quantum efficiency and excellent thermal stability. The luminescent intensity of Ca₂PO₄Cl:Eu²⁺ was found to be 128% under excitation at 380 nm, 149% under 400 nm, and 247% under 420 nm as high as that of BaMgAl₁₀O₁₇:Eu²⁺. The optimal doping concentration was observed to 11 mol.% of CAP:Eu²⁺. The energy transfer between Eu²⁺ ions in CAP were occurred via electric multipolar interaction, and the critical transfer distance was estimated to be 1.26 nm. A mixture of blue-emitting Ca₂PO₄Cl:Eu²⁺, green-emitting (Ba,Sr)₂SiO₄:Eu²⁺ and red-emitting CaAlSiN₃:Eu²⁺ phosphors were selected in conjunction with 400 nm chip to fabricate white LED devices. The average color-rendering index R_a and correlated color temperature (T_c) of the white LEDs were found to be 93.4 and 4590 K, respectively. The results indicated that it was a promising candidate as a blue-emitting phosphor for the near-UV white light-emitting diodes.     

Synthesis and optical properties of novel apatite-type NaCa3Bi(PO4)3F:Dy3+ yellow-emitting fluorophosphate phosphors for white LEDs

In this study, novel yellow-emitting fluorophosphate NaCa₃Bi(PO₄)₃F phosphors doped with different concentrations of Dy³⁺ ions were first obtained via high-temperature solid-state reaction. The crystal structure, phase purity, particle morphology, photoluminescence (PL) properties, thermal stability, and luminescence decay curves of the resulting phosphors were then characterized in detail. Under the excitation of 349 nm, the three dominant peaks of the NaCa₃Bi(PO₄)₃F:Dy³⁺ are centered at 480 nm (⁴F_9/2-⁶H_15/2), 577 nm (⁴F_9/2-⁶H_13/2), and 662 nm (⁴F_9/2-⁶H_11/2). The optimal doping concentration of Dy³⁺ ions in the NaCa₃Bi(PO₄)₃F:xDy³⁺ phosphors is x = 5 mol%. The phosphors show excellent thermal stability with high activation energy (E_a = 0.32 eV). Eventually, the synthesized white light-emitting diode (w-LED) demonstrates the Commission International de L'Eclairage (CIE) chromaticity coordinates of (0.341, 0.334), a good correlated color temperature (CCT) of 5083 K, and a high color rendering index (R_a) of 92. Revealing its potential as yellow-emitting phosphors, the feasibility of the fabricated apatite-type NaCa₃Bi(PO₄)₃F:Dy³⁺ fluorophosphate phosphors was confirmed for w-LEDs.     

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.     

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.     

Luminescence properties of red phosphors Ca_（10）Li（PO_4）_7：Eu~（3＋）

A series of red phosphors Ca10Li (PO4)7:Eu3+ were synthesized by high temperature solid-state reaction method. Their luminescence properties were characterized by means of photoluminescence excitation and emission spectra,CIE chromaticity and quantum efficiency. Results indicated that the phosphors could be effectively excited by the near ultraviolet (NUV) light (393 nm). The main emission peaks of the phosphor were ascribed to the transition 5D0-7F2 (613 and 617 nm) of Eu3+ ion when samples were excited by...     

Enhanced luminescence efficiency and thermal stability via introduction of non-rare earth Bi3+ in Gd5Si2BO13:Eu3+

A series of Gd₅Si₂BO₁₃:Eu³⁺ and non-rare earth Bi³⁺ ions doped Gd₅Si₂BO₁₃:Eu³⁺ phosphors was successfully synthesized via high-temperature solid-state method,and the as-obtained phosphors were studied on their phase structures,luminescence characteristics,thermal stability and luminescence lifetime.Transient fluorescence spectroscopy data show that the addition of Bi³⁺ can obviously enha...     

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.     

Green and red phosphor for LED backlight in wide color gamut LCD

Wide color gamut(WCG) backlight for liquid crystal display(LCD) utilizing white light-emitting diodes(LED) has attracted considerable attention for their high efficiency and color reduction.In this review,recent developments in crystal structure,luminescence and applications of phosphors for wide color gamut LED backlight are introduced.As novel red phosphors,Mn~(4+)activate fluoride and aluminate phosphors are advanced in quantum efficiency,thermal quenching and color saturation for their characteristic spectrum with broad excitation band and linear emission.The crystal structure and fluorescence properties of Mn~(4+)doped fluosilicate,fluorogermanate,fluotitanate,as well as Sr_4 Al_(14)O_(25),CaAl_(12)O_(19) and BaMgAl_(10)O_(17) phosphors are discussed in detail.A serial of narrow-band red-emitting Eu~(2+),Eu~(3+)and Pr~(3+)-doped nitride silicates and molybdate phosphors are also introduced.Rare-earth-doped oxynitride and silicate green-emitting phosphors have attracted more and more attention because of the wide excitation,narrow emission,high quenching temperature,high quantum efficiency,such as β-sialon:Eu~(2+),Ba_3Si_6O_(12)N_2:Eu~(2+),MSi_2O_2N_2:Eu~(2+)(M=Ca,Sr,Ba),y-AlON:Mn~(2+)and Ca_3Sc_2Si_3O_(12):Ce~(3+).All above phosphors demonstrate their adaptability in wide color gamut LCD display.Especially for Mn~(4+)doped fluosilicate red phosphor and β-sialon:Eu~(2+)green phosphor.To achieve an ultra-high color gamut in white LED backlight and against the OLED,innovative narrow-band-emission red and green phosphor materials with independent intellectual property rights are continuously pursed.     

Plasmon-enhanced broad-band quantum-cutting of NaBaPO4:Eu2+,Er3+ phosphors with silver nano-particles

NaBaPO₄:Eu²⁺,Er³⁺ phosphors and Ag nano-particles (NPs) were prepared by the solid-state reaction and chemical reduction method, respectively. The fluorescence spectra and decay curves demonstrate the effective energy transfer from Eu²⁺ to Er³⁺ and the existence of three-photon quantum-cutting through two-step cross-relaxation of Er³⁺. The quantum-cutting emission is peaked at 1534 nm with a broad excitation band centered at 352 nm. Plasmon-enhanced quantum-cutting of NaBaPO₄:Eu²⁺,Er³⁺ phosphors was realized by decorating Ag NPs. The largest enhancement factor is 1.395. It is hopeful to improve the photovoltaic conversion efficiency of Ge solar cells by using this phosphor.     

Synthesis and optical properties of novel double perovskite Ca_2MgTeO_6:Dy~(3+),Na~+ phosphors for white LEDs

Novel yellow-emitting phosphors of Dy~(3+)-doped double perovskite Ca_2 MgTeO_6 were synthesized by using a conventional high-temperature solid-state reaction.The phase purity,particle morphology,size distribution,elemental composition,luminescence properties,and luminescence decay curves of the resulting products were then analyzed in detail.The Ca2 MgTeO_6:Dy~(3+),Na~+ phosphors show three emission peaks after near-ultraviolet excitation at 350 nm,which correspond to ~4 F_(9/2)→~6 H_(11/2),~4 F_(9/2)→~6 H_(13/2),and ~4 F_(9/2)→~6 H_(13/2) transitions,respectively.Among them,the strongest peak is observed at 573 nm.The best doping content of Dy~(3+)in Ca_2 MgTeO_6:xDy~(3+),xNa~+ phosphors is x=5 mol%.The calculated critical distance of energy transfer between Dy~(3+) ions is 1.6 nm.Luminescence quenching is confirmed to be due to dipole-dipole interactions among Dy~(3+) ions.The phosphors show excellent thermal stability with high activation energy(0.27 eV).The Commission Internationale de l'Eclairage(CIE) chromaticity coordinates of the Ca_2 MgTeO_6 Dy~(3+),Na~+ phosphors are located in the yellow region.White light-emitting diodes(w-LEDs) were fabricated with a high color rendering index(R_a) of 88 and a good correlated color temperature(CCT) of 5440 K.All observed properties indicate that Ca_2 MgTeO_6:Dy~(3+),Na~+ phosphors have potential applications in display and photonic devices.     

Effect of excitation wavelength (blue vs near UV) and dopant concentrations on afterglow and fast decay of persistent phosphor SrAl2O4:Eu2+,Dy3+

The persistent phosphor SrAl₂O₄:Eu²⁺,Dy³⁺ is the subject of numerous investigations. One often neglected aspect is that in this phosphor, as well as in Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, there are two different Sr²⁺ sites which can be occupied by the dopant Eu²⁺ ions. We first introduce a general scheme of possible energy transfers in these persistent phosphor materials including explicitly both europium ions. This scheme is used as a generic starting point to study experimentally specific pathways. We illustrate this application with the study of the effect of excitation wavelength (444 and 382 nm) on the afterglow of differently doped SrAl₂O₄:Eu²⁺,Dy³⁺ samples, as well as on the emission decay curves. With the same excitation intensity under 444 nm excitation, the resulting afterglow intensity is stronger than under near UV excitation. At 382 nm, Eu²⁺ ions on both Sr²⁺ sites in SrAl₂O₄ are excited, but at room temperature the blue emission is quenched, leading to a loss of photons. The observed effects can further be associated with the ratio of Eu²⁺ ions and trap states which are modulated by the concentrations of Eu²⁺ and Dy³⁺ in SrAl₂O₄, as well as by temperature. Increasing the nominal Dy³⁺ content from 0.1 mol% to 0.5 mol% with respect to Sr results in the doubling of the integrated afterglow intensity and confirms thus that Dy³⁺ ions are indeed involved in the trapping process. The concentration of trap states is much lower than the concentration of Eu²⁺ ions, as even with low excitation densities, a plateau of integrated afterglow intensity (corresponding to the total number of accessible traps) is reached. We postulate that an important fraction of excited Eu²⁺ ions can potentially transfer their energy to trap states. Once that all traps are filled or in a dynamical filling-depletion process under illumination (with thermal and/or optical depletion processes), for the remaining Eu²⁺ a “normal” steady-state emission is observed. The luminescence decay curves at 520 nm measured at 77 K show a mono-exponential decay with a common lifetime of about 1140 ns for all 5 samples under 437 nm excitation, while under 375 nm excitation, a feed process originating from the energy transfer between Eu²⁺ ions is demonstrated. Under 375 nm excitation, the non-exponential decay observed at 440 nm can be quantitatively associated to a Förster energy transfer process with R₀ = 1.58 (8) nm. For the overall understanding of the afterglow processes, it appears that one has to consider the individual contributions of all active ions on different lattice sites.     

Physicochemical properties of Li3Ba2La3(MoO4)8:Eu,Tb red-emitting phosphor for solid state white lamps

In this work,combustion synthesis was used for the first time to fabricate a phosphor material with red emission for applications in solid-state white-light lamps.We synthesized a material with emission wavelength at λ_em=617 nm,excited under long UV-blue wavelength based on Eu³⁺,Tb³⁺-activated molybdates Li₃Ba₂(La_1-x-yEu_xTb_y)₃(MoO₄)₈ with 0 ≤ x ≤1 and 0 ≤ y ≤ 1.A series of pow...     

Preparation of Eu2+,Dy3+,Zr4+ ions co-doped strontium aluminate/molybdate multi-optical functional hybrid pigments for anti-counterfeiting

Eu²⁺,Dy³⁺ and Zr⁴⁺ ions co-doped strontium aluminate(i.e.,SrAl₂O₄:Eu²⁺,Dy³⁺,Zr⁴⁺)/molybdate(i.e.,Ho₂MoO₆ or Nd₂MoO₆) with photo-/mechano-luminescence and allochroic effect as multi-optical functional hybrid pigments were prepared via solid state reactions and subsequent mixing.The phosphor and hybrid pigments were characterized by X-ray diffraction,scanning electron...