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 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℃.     

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.     

Color tunable and white light emitting via energy transfer in single-phase BiOCl:Er3+,Sm3+ phosphors for WLEDs

BiOCl crystal shows potential as efficient optical host due to its special layered structure. Here,the luminescence properties of the Er~(3+)/Sm~(3+) co-doped BiOCl phosphors as single-phase phosphors were reported. Upon near ultraviolet excitation(NUV, 380 nm corresponding the ~4 I_(15/2)→ ~4 G_(11/2) transition of Er~(3+) ions), the phosphors exhibit the efficient characteristic emissions of Er~(3+) and Sm~(3+) ions simultaneously. The energy transfer(ET) from Er~(3+) to Sm~(3+) ions in the layered crystals has been validated by the variation of emission intensities and decay lifetimes respectively, which is ascribed to be a dipoledipole interaction. By virtue of the ET behavior and increasing Sm~(3+) ion concentration, the enhancing emission intensity of Sm~(3+) and the tunability of emission color from yellowish-green(0.318, 0.420) to white(0.343, 0.347) are realized. The results of our work indicate that the Er~(3+)/Sm~(3+) co-doped BiOCI phosphor has a promising application serving as single component white emitting phosphors for NUV excited WLEDs.     

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.     

Enhanced afterglow performance of CaAl_2O_4:Eu~(2+),Nd~(3+) phosphors by co-doping Gd~(3+)

In order to effectively improve the afterglow properties of CaAl_2 O_4:Eu~(2+),Nd~(3+) phosphors,a series of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)(x=0,0.012,0.024,0.036,0.048,0.060 mol) phosphors were prepared by a high-temperature solid-phase approach.Crystalline composition and microstructure were characterized by XRD,TEM,HRTEM,and XPS,luminescence properties were systematically analyzed by fluorescence spectra,afterglow decay curves and TL glow curve.Results show that all of Ca_(0.982-x)Al_2 O_4:0.012 Eu~(2+),0.006 Nd~(3+),xGd~(3+)phosphors belong to monoclinic CaAl_2 O_4,without other cystalline phase.The blue emission at 442 nm is observed,which is assigned to the 4 f~65 d→4 f~7 transition of Eu~(2+) ions.Doping with appropriate amount of Gd~(3+) ions(x=0.036 mol) significantly improves the afterglow properties of phosphors,but the excessive doping of Gd~(3+) induces the fluorescent quenching.The doping of moderate Gd3+changes the traps states,the trap depth varies from 0.598 to 0.644 eV and the trap concentration is also greatly improved,thus significantly improving afterglow performance.     

Enhanced luminescence performances of Mn~(4+)-activated Sr_4Al_(14)O_(25) red phosphors by doping with Sc~(3+) ions

A series of non-rare earth Mn⁴⁺-activated strontium aluminate phosphors Sr₄Al₁₄O₂₅:Mn⁴⁺co-doped with Sc³⁺ions were successfully synthesized by a high-temperature solid-state reaction method.XRD result reveals that there is no introduction of additional phase but expansion of lattice with incorporation of Sc34 ions.Excitation and emission spectrum measurement shows that the synthesized phosphors can be efficiently excited by near-ultraviolet and blue light,and a deep red emission centered at 652 nm with a narrow full width at half maximum(FWHM)can be obtained,which is attributed to the transition²E→⁴A₂of Mn⁴⁺ions.In addition,the crystal field strength parameter(Dq)and Racah parameters(B,C)and energies of states were calculated based on experimental data.Moreover,the luminous intensity of Sr₄Al_14-xSCxO₂₅:Mn⁴⁺is enhanced and increased by 60%compared with Mn⁴⁺single incorporated sample at x=0.06.A phenomenon of redshift is observed in the excitation spectrum and discussed systematically.Finally,the mechanism of the positive effects with Sc³⁺ions incorporated into lattice is discussed in detail.All the results suggest that the Sr₄Al_13.94Sc_0.06O₂₅:Mn⁴⁺phosphor will become one of the great candidates for backlight of LCD.     

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.     

Energy transfer mechanism of Sr_4Al_(14)O_(25):Eu~(2+) phosphor

Long lasting blue-green-emitting Sr4Al14O25:Eu2+ phosphors were synthesized by solid-state reactions.The phosphors were investigated by X-ray diffraction(XRD) and fluorescence spectrophotometer.A pure phase of Sr4Al14O25:Eu2+ phosphor was obtained at 1250 °C.There are two different types of Eu emission centers in Sr4Al14O25:Eu2+ phosphor.The effects of the Eu2+ concentration and the reducing temperature on the distribution of Eu2+ among different sites were investigated.The energy transfer mechanism between two different emission centers was elucidated via the investigation of thermal damage influence on the phosphorescence spectra,that is,the energy emitted from an Eu1 emission center could be reabsorbed by an Eu2 emission center.     

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.     

Blue-green BaAl_2O_4：Eu~（2＋）,Dy~（3＋） phosphors synthesized via combustion synthesis method assisted by microwave irradiation

Blue-green luminescent BaAl2O4:Eu2+,Dy3+ phosphor powders were synthesized via combustion synthesis method assisted by microwave irradiation in air. The phosphors were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectrophotometer. The XRD results revealed that when the concentration of urea was over 3 times higher than theoretical quantities, a BaAl2O4 single hexagonal phase was obtained. The SEM results revealed that the surface of the BaAl2O4:Eu2+,Dy3+ pow...     

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＋.     

Electron Transition of Eu~(2+) and Energy Transfer in Crystals BaFX:Eu~(2+),Eu~(3+) (X=Cl,Br)

In crystals BaFX:Eu~(2+)(X=Cl,Br).there exists configuration interaction between 4f~65d and 4f~65s ex-cited state of Eu~(2+)ion.and it results in the change of relative intensities of d-f and f-f transition.The transition~S_-_2→4f~65d-6s is observed.The variation of F/X atomic ratio between 110/90 and 90/110 does not obvi-ously influence the luminescence of BaFX:Eu~(2-).There is energy transfer between Eu~(2+)(f-f)and Eu~(3+)whichcoexists in the matrices.     

Synthesis and characterization of Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+) nanorods via a solvothermal routine

Y2O2S:Eu3+,Mg2+,Ti4+ nanorods were prepared by a solvothermal procedure.Rod-like Y(OH)3 was firstly synthesized by hydrothermal method to serve as the precursor.Y2O2S:Eu3+,Mg2+,Ti4+ powders were obtained by calcinating the precursor at CS2 atmosphere.The Y2O2S:Eu3+,Mg2+,Ti4+ phosphor with diameters of 30-50 nm and lengths up to 200-400 nm inherited the rod-like shape from the precursor after calcined at CS2 atmosphere.The Y2O2S:Eu3+,Mg2+,Ti4+ nanorods showed hexagonal pure phase,good dispersion and exhibite...     

Photoluminescence properties and thermal stability of Eu~(3+)-activated La_7Ta_3W_4O_(30) red-emitting phosphors for near-UV-excited w-LEDs

Novel trivalent europium(Eu~(3+))-activated La_7 Ta_3 W_4 O_(30):xEu~(3+)(x=0.5 mol%-40 mol%) red-emitting phosphors were synthesized by means of a high-temperature solid-state reaction.The structure,morphology,photoluminescence,thermal-stability properties,lifetime,and color-rendering of the prepared phosphors were investigated in detail.The La_7 Ta_3 W_4 O_(30):Eu~(3+) phosphors show five emission peaks under near-ultraviolet(n-UV) at 397 nm,and these peaks are ascribed to the transitions of ~5 D_0-~7 F_j(j=0,1,2,3 and 4) by Eu~(3+) ions.The optimal doping concentration of Eu~(3+) is 20 mol%,and the critical distance of the energy transfer between the Eu3+ions was calculated to be 1.768 nm.The quenching temperature(T_(0.5)) of La_7 Ta_3 W_4 O_(30):20 mol%Eu~(3+) is about 440 K.The quantum yield(QY) was measured to be 85.85%.The fabricated white-light-emitting diodes(w-LEDs) possess high color-rendering index(R_a) of 90,and high correlated color temperature(CCT) of 5810 K,respectively.The Commission Internationale de L'Eclairage(CIE) coordinates are(0.311,0.322).Therefore,the prepared phosphor has a promising application for w-LEDs.     

SrAl_2O_4:Eu~(2+),Dy~(3+)的发光性质及机理

研究了Eu2＋、Dy3＋共激活的SrAl2O4体系的发光性能和能量传输。结果表明，Dy3＋、Eu2＋共存时，Eu2＋的发光强度远远大于无Dy3＋时的发光强度，证明Dy3＋对Eu2＋的发光有敏化作用。Dy→Eu2＋能量传输的方式为籍助于载流子的能量输运。     

Photoluminescence of Eu~(2+)-activated Na_(1-x)Al_(1-x)Si_(1+x)O_4 upon UV excitation

A convenient high temperature solid-state reaction method was developed to fabricate Na1-xAl1-xSi1+xO4:Eu2+ phosphors.The as-prepared products were characterized by X-ray diffraction(XRD),photoluminescence(PL),and photoluminescence excitation(PLE).The luminescence of Na1-xAl1-xSi1+xO4:Eu2+ phosphors were characterized by the two corresponding emission centers at 535 and 440 nm.The excitation spectrum extended from 250 to 400 nm.A white light was observed by naked eye upon ultraviolet excitation.The relative...     

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+).     

Structural and optical properties of Dy~(3+):YAlO_3 phosphors for yellow light-emitting diode applications

The spectroscopic properties of a series of Dy~(3+) single-doped and Dy~(3+)/Nd~(3+),Dy~(3+)/Tb~(3+),and Dy~(3+)/Tm~(3+)co-doped YAlO_3(yttrium aluminum perovskite,YAP) phosphors were investigated and compared through the measurements of optical absorption,emission spectra,and fluorescence decay curves.For the Dy~(3+) ion single-doped samples,the intensity of each absorption band increases with an increment in Dy~(3+) ion doping concentration,and the identified strong absorption peak at 447 nm indicates that Dy~(3+):YAP phosphors are suitable to be pumped by a blue laser diode(LD).For all co-doped samples,absorption peaks of Dy~(3+) ion along with some of the absorption bands of Nd~(3+),Tb~(3+),and Tm~(3+) ions are observed.Under 351 and 447 nm excitation,a prominent emission peak at 572 nm was obtained in all the samples,corresponding to Dy~(3+):~4 F_(9/2)→~6 H_(13/2) transition.Here,2 at% Dy~(3+):YAP phosphor exhibits the highest yellow emission intensity under 447 nm pumping.Among the three kinds of Dy~(3+) co-doped phosphors,Dy~(3+)/Tb~(3+):YAP phosphor possesses the dominant yellow emission.The fluorescence decay curves show exponential behaviour and are fitted well.The Commission International de L'Eclairage(CIE)chromaticity coordinates were calculated following the respective emission spectra,and it is found that all the coordinates locate in the yellow region.The energy transfer(ET) processes were investigated and the concentration quenching mechanism was discussed.The obtained results suggest that Dy~(3+)-activated YAP phosphors are good candidates for yellow LED applications.     

Rational design of monovalent ions (Li,Na,K) co-doped ZnAl_2O_4:Eu~(3+) nanocrystals enabling versatile robust latent fingerprint visualization

Alkali metal ions(M~+ = Na~+,Li~+,K~+) co-doped ZnAl_2O_4:Eu~(3+)(5 mol%)(ZAE) nanopowders(NPs) were prepared via solution combustion route using Mimosa pudica(MP) leaves extract as a fuel. PXRD results of co-doped samples enhance the crystallinity and grain growth. Photoluminescence(PL) of the prepared ZAE and ZAE:M~+(M~+ = Na~+, Li~+, K~+) NPs shows intense emission peaks in the range of 550-750 nm and ascribed to ~5D_0→~7F_J(J=0-4) transitions of Eu~(3+) ions, respectively. A 2-fold enhancement in PL intensity was observed in Li~+ co-doped samples. The optimized ZnAl_2O_4:Eu~(3+)(5 mol%), Li~+(1 wt%)(ZAEL)NPs were used to visualize LFPs on various porous, semi-porous and non-porous surfaces through robust powder dusting technique. The visualized latent fingerprints(LFPs) reveal well defined level 1-3 ridge characteristics under several tests such as fingerprint aging and fresh water treatment for various time durations. The obtained results clearly evidence that the prepared NPs are quite useful for multifunctional applications such as advanced forensic and solid state lightning.