Tunable luminescence,energy transfer and excellent thermal stability of SrMg_2(PO_4)_2:Ce~(3+),Tb~(3+) phosphors for LEDs

A series of novel SrMg_2(PO_4)_2:Ce~(3+),Tb~(3+)(SMP:Ce~(3+),Tb~(3+)) phosphors with tunable emission spectra were produced via high temperature solid phase method.XRD,fluorescence spectrum and fluorescence lifetime for SMP:Ce~(3+),Tb~(3+)were studied in detail.Under the excitation at 308 nm,SMP:Ce~(3+),Tb~(3+) samples can emit high efficiency tunable blue-green light by controlling the proportion of dopant concentration.Through the spectral overlap and the regular change of fluorescence lifetime,it is proved that there is a significant energy transfer between Ce~(3+) and Tb~(3+) in SMP matrix and the energy transfer mechanism is determined to be an electric dipole-dipole interaction with energy transmission efficiency of 55%.In additional,Commission International de L'Eclairage(CIE) color coordinates and thermal stability were studied.All above findings suggest that SMP:Ce~(3+),Tb~(3+)can be regarded as the potential bluish green phosphor for LED applications.     

Luminescence and energy transfer of color-tunable Lu_2MgAl_4SiO_(12):Eu~(2+),Ce~(3+),Mn~(2+) phosphors

Energy transfer among the co-doped activators is an efficient route to achieve color-tunable emission in inorganic phosphors.Herein,photoluminescence tuning from blue to cyan has been achieved in the Lu_2MgAl_4 SiO_(12);Eu~(2+),Ce~(3+)phosphors by varying the Ce~(3+) concentration with a fixed Eu~(2+)content.With the further introduction of a Mn~(2+)-Si4+couple into the host lattice,the emission color can be tuned to red through the energy transfer of Eu~(2+)and Mn~(2+).The luminescence properties and the energy transfer mechanism were studied in detail.The energy transfer from Eu~(2+)to Ce~(3+)is certified as a dipolequadrupole interaction with the energy transfer efficiency of 41.4% and Eu~(2+)to Mn~(2+)belongs to a dipole-dipole interaction with the energy transfer efficiency of 94.3%.The results imply that this singlephased Lu_2MgAl4 SiO_(12):Eu~(2+),Ce~(3+),Mn~(2+)phosphor has a potential prospect for application in near-UV chip pumped 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.     

Broadband near-infrared luminescence and energy transfer of Cr~(3+),Ce~(3+) co-doped Ca_2LuHf_2Al_3O_(12) phosphors

Broadband near-infrared phosphors are highly desirable for food testing.Targeted Ca₂LuHf₂Al₃O₁₂:Cr³⁺(CLHA:Cr³⁺) and Ca₂LuHf₂Al₃O₁₂:Ce³⁺,Cr³⁺(CLHA:Ce³⁺,Cr^(³⁺)) phosphors were synthesized by the conventional high-temperature solid state reaction.The CLHA:Cr³⁺phosphor,with a good thermal stability,shows a red shift owing to radiation reabsorption and non-radiative transition with increasing Cr³⁺content.For co-doped sample,the emission intensity of Cr³⁺can be enhanced by three times due to the energy transfer from Ce³⁺to Cr³⁺,which can be evidenced by a significant overlap between the PLE of Cr³⁺single-doped phosphor and the PL of Ce³⁺single-doped phosphor.In addition,the mechanism of energy transfer is identified as a quadrupole-quadrupole interaction according to decay Lifetime and Dexter’s energy transfer formula.The broadband NIR emission peaked at 775 nm of CLHA:Cr³⁺,Ce³⁺phosphor shows a bright prospect in nondestructive quality-control analysis systems for food.     

Tunable luminescence and energy transfer in Y_2BaAl_4SiO_(12):Tb~(3+),Eu~(3+)phosphors for solid-state lighting

Single-phase Y₂BaAl₄SiO₁₂:Tb³⁺,Eu³⁺phosphors with adjustable luminescence were successfully prepared by high-temperature solid-state reaction method.The structural,luminescent properties and ene rgy transfer(ET) process of Y₂BaAl₄SiO₁₂:Tb^(³⁺),Eu³⁺phosphors were syste matically analyzed with the help of X-ray diffraction(XRD),scanning electron microscopy(SEM),excitation spectra,emission spectra and photoluminescence decay curves.Tunable luminescence ranging from green through yellow and definitively to red can be achieved by elevating amounts of Eu³⁺ions in Tb³⁺,Eu³⁺co-doped samples.Besides,the ET mechanism and efficiency were also analyzed and the maximum ET efficiency is 67%.All the results show that Y₂BaAl₄SiO₁₂:Tb³⁺,Eu³⁺phosphors can be used in solid-state lighting.     

Luminescent properties and energy transfer of color-tunable Sr3Y2（SiO3）6：Ce3＋,Tb3＋ phosphors

Phosphors with controlled emission spectra are of great interest due to their application for white light emitting diodes.Herein, a new class of Sr3Y2（SiO3）6：Ce3＋,Tb3＋ phosphors were synthesized by a facile sol-gel combustion method. The phase structure,morphology, and luminescence properties of the phosphors were characterized by using powder X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, and photoluminescence excitation and emission spectra,respectively. The results on luminescence properties indicated that co-doped Ce3＋ ions served as UV-light sensitizers with excitation energy partially transferred to Tb3＋ ions, leading to green emission from Tb3＋. Particularly, the corresponding emitting colors of the phosphors could be well-tuned from deep blue（0.16, 0.05） to green region（0.25, 0.45） by adjusting the molar ratio of Ce3＋/Tb3＋.     

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.     

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.     

Photoluminescence properties of Tm~(3+)/Tb~(3+)/Sm~(3+)tri-doped Na_5Y_9F_(32)single crystal with high thermal stability for white light-emitting diodes

A novel Tm~(3+)/Tb~(3+)/Sm~(3+)tri-doped Na_5 Y_9 F_(32) single crystal was synthesized by a modified Bridgman method for the propose of white light emitting diodes.The fluorescence spectra of various Sm~(3+)ion concentrations and fixed 0.4 mol% Tm~(3+) and 0.5 mol% Tb~(3+) were measured and studied systematically excited by near-ultraviolet light of 355 nm.The Sm3+ion concentration takes apparent effect on the relative intensity of peaks in the visible region and the color coordinate combining from these emission bands.A near pure white light emission with color coordinates(0.3295,0.3057) and color temperature(5657 K) can be obtained when the concentrations of Tm~(3+),Tb~(3+) and Sm~(3+) ions are 0.4 mol%,0.5 mol%and 0.8 mol%,respectively.Furthermore,the practical down-conversion internal quantum yield was measured by integrating spheres at about 14.39%.The tri-doped Na_5 Y_9 F_(32) single crystal shows a high thermal stability inferring from the temperature dependent emission in which the integrated emission intensities are reduced only by～3% with the increase of temperature from 280 to 450 K.The present results demonstrate that the Tm~(3+)/Tb~(3+)/Sm~(3+)tri-doped Na_5 Y_9 F_(32) single crystal may provide a promising candidate for white light-emitting diodes,luminescent materials and fluorescent display devices.     

Emission tunable of Mg_(0.695)Si_(0.695)Al_(1.39)O_(3.65)N_(0.35):Eu~(2+),Mn~(2+) oxynitride phosphors via energy transfer for WLEDs

A series of Eu~(2+)doped and Eu~(2+)/Mn~(2+) co-doped Mg_(0.695)Si_(0.695)Al_(1.39)O_(3.65)N_(0.35)(MSAON) phosphors were synthesized by solid-state reaction at a lower temperature of 1500℃.The crystal morphology and structure of MSAON host were characterized by SEM,TEM and XRD.The quantum yield(QY) for Eu~(2+)doped MSAON phosphors was measured as high as 62%,indicating the excellent luminous efficiency.For the Eu~(2+)/Mn~(2+)co-doped MSAON phosphor,the photoluminescence spectrum and delay curves reveal the efficient energy transfer(ET) process from Eu2+to Mn~(2+)ions.Meanwhile,the corresponding energy transfer efficiency,critical distance and mechanism are discussed in detail.Temperature-dependent emission spectrum shows the thermal and color stabilities.The emission color of MSAON:Eu~(2+),Mn~(2+)phosphors could be tuned from blue through white to red via varying the concentration of Mn~(2+) ions.White-light-emitting diodes(WLEDs) were successfully fabricated by encapsulating the phosphors in nUV LED(365 nm) devices obtaining white light with color rendering index(CRI) as high as 87.7.The results reveal that the MSAON:Eu~(2+),Mn~(2+)phosphors could have potential application in the field of n-UV WLEDs.     

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.     

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.     

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.     

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.     

Sensitizing effect of Nd~(3+) on Tb~(3+) activated ZrP_2O_7 long persistent phosphor materials

The long persistent phosphors of Zr_(0.97)P_2 O_7:0.018 Tb~(3+),0.012 Nd3+with Nd~(3+)as sensitized ions and Tb~(3+)as emission centers were synthesized using high temperature solid state reaction.The crystal structure and defects,excitation and emission spectra,decay curves and thermoluminescence(TL) curves of the phosphors were investigated.The synthesized Zr_(0.97)P_2 O_7:0.018 Tb3+,0.012 Nd3+is essentially in line with the standard card PDF#49-1079.The emission band with main peak at 548 nm exhibits the characteristic transitions of ~5 D_3-~7 F_j(j=5,4) and ~5 D3-~7 F_j(j=6,5,4,3) of Tb~(3+).The analysis of excitation and emission spectra shows that there exists the overlap between the emission peaks of Nd~(3+)at 466 and 485 nm and the excitation of Tb3+at 443 and 485 nm,and the energy transfer from Nd3+to Tb3+plays an important role in the improvement of luminescence properties.The decay curves shows that Zr_(0.97)P_2 O_7:0.018 Tb3+,0.012 Nd3+has longer afterglow time than ZrP_2 O_7 and Zr_(0.982)P_2 O_7:0.018 Tb3+.Additionally,the TL curves indicate that the trap depth at 0.72 eV in Zr_(0.97)P_2 O_7:0.018 Tb~(3+),0.012 Nd3+is to the benefit of the afterglow time.The possible luminescence mechanism of ZrP_2 O_7:Tb~(3+),Nd3+is proposed on the basis of the XPS spectra,EPR spectra,excitation and emission spectra,decay curves,TL curves and the analysis of defect equations.     

Glass forming regions and concentration-dependent luminescence properties of Tb~(3+)-activated tellurium-lutetium-tungsten glasses

The glass-forming regions of tellurium-gadolinium-tungsten ternary system prepared at 1000℃for 60 min were firstly determined.To improve density,the full replacement of lutetium for gadolinium to form Tb³⁺-activated tellurium-lutetium-tungsten glasses with the composition of 64 TeO₂-20 WO₃-(16-y)Lu₂O₃-yTb₂O₃were designed for scintillation application.The concentration-dependent optical properties of Tb³⁺-activated tellurium-lutetium-tungsten glasses were fully investigated by transmittance,excitation and emission spectra,together with the luminescence decay curves.The energy transfer mechanism was discussed according to Huang’s rule.The optimized 4 mol%Tb₂O₃activated tellurium-lutetium-tungsten glasses with the density of 6.49 g/cm³and the lifetime of 0.551 ms are developing to be suitable for the potential detection of slow events in the future work.     

Luminescence tuning of Ce~(3+),Pr~(3+) activated(Y,Gd)AGG system by band gap engineering and energy transfer

Tuning of phosphor luminescence properties,including the emission energy/intensity and thermal stability,is an important way to develop superior luminescent materials for diverse applications.In this work,we discuss the effect of band gap engineering and energy transfer on the luminescence properties of Ce~(3+)or Pr~(3+) doped(Y,Gd)AGG systems,and analyze the underlying reasons for their different phenomena.By using VUV-UV excitation spectra and constructing VRBE schemes,the changes of host band structure,5 d excited level energies and emission thermal stability of Ce~(3+)and Pr~(3+) with the incorporation of Gd~(3+)ions were studied.In addition,the energy transfer dynamics was also investigated in terms of the luminescence decay curves.This work demonstrates a way to tune phosphor luminescence properties by combining band gap engineering and energy transfer tailoring and provides an inspiring discussion on the different results of Ce~(3+)doping on the Ce~(3+)and Pr~(3+)emissions.     

Significant enhancement of blue photoluminescence intensity of Dy~(3+) modified Sr_6Ca_4(PO_4)_6F_2:Eu~(2+) phosphors

Blue-emitting phosphors Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+)(SCPF:Eu~(2+)),Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+),Dy~(3+)(SCPF:Eu~(2+),Dy~(3+))and Sr_6 Ca_4(PO_4)_6 F_2:Eu~(2+),Dy~(3+),Si~(4+)(SCPF:Eu~(2+),Dy~(3+),Si~(4+)) with apatite structure were successfully synthesized by traditional solid-state reaction under reducing atmosphere.Eu~(2+),Dy~(3+) and Si4+ions occupy the corresponding sites of Sr~(2+),Ca~(2+) and P~(5+).Strong broad blue photo luminescence band is exhibited in SCPF:Eu~(2+),Dy~(3+) phosphor ranging from 400 to 550 nm centered at 455 nm and Dy~(3+) ions are vital in creating traps.Emission intensity of Eu~(2+),Dy~(3+) co-doped SCPF:0.02 Eu~(2+),0.02 Dy~(3+) is about 1.8 times that of SCPF:0.02 Eu~(2+) and electron trap centers serve as energy transporting media.To further elucidate the formation and effect of the specific defect on the luminescence of SCPF:0.02 Eu~(2+),0.02 Dy~(3+) phosphor,the thermoluminescence properties,decay curves and thermal stability studies were performed while the Si~(4+)-P~(5+) charge compensated pho sphor SCPF:0.02 Eu~(2+),0.02 Dy~(3+),0.02 Si~(4+) was prepared as a contrast.All the results of present work indicate that Dy~(3+) co-doping can obviously enhance photoluminescence intensity of SCPF:0.02 Eu~(2+) by the electron traps generated by non-equivalence replacement of Dy~(3+)-Ca~(2+).     

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...     

Preparation and characterization of NaYF_4:Er~(3+),Tm~(3+)@NaYF_4:Ce~(3+),Tb~(3+) microcrystals with dual-mode emissions at the single-particle level

Under hydrothermal environment,we synthesized lanthanide ions doped sodium yttrium fluoride(NaYF₄:Er,Tm@NaYF₄:Ce,Tb) luminescent microcrystals via an epitaxial growth technique.The structure and morphology of these microcrystals were examined by SEM,TEM,EDS and XRD measurements.These particles show dual-mode emissions with red upconversion(UC) and green down conversion(DC) as single particles level.The mean length and diameter of these microparticles increase from 0.43 to2....