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+).     

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.     

Effect of light conversion agent on luminous properties of a new down-converting material SrAl_2O_4:Eu~(2+),Dy~(3+)/light conversion agent

A new luminous material SrAl_2O_4:Eu~(2+),Dy~(3+)/light conversion agent that can emit red light in the darkness after being excited was fabricated by combining light conversion agent on to SrAl_2O_4:Eu~(2+),Dy~(3+) particles through YsiX3.The morphology of the luminous materials was analyzed by scan electron microscopy(SEM).The emission behavior was evaluated by fluorescence spectrophotometric analysis and the results demonstrated that the emission spectra of samples had a redshift compared to SrAl_2O_4:Eu~(2+),Dy~(3+) and the emission intensity rose dramatically at first and then decreased when the ratio of light conversion agent doping was over 1.4 wt.%.And the emission color of SrAl_2O_4:Eu~(2+),Dy~(3+)/light conversion agent was tuned from green(SrAl_2O_4:Eu~(2+),Dy~(3+))to orange-red.Furthermore,the afterglow property was also investigated,and the results indicated that the afterglow brightness reached 6.5 cd/m~2,and as the light conversion agent concentration increased the brightness intensity decreased.     

Optical performance study of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+) ternary luminous fiber

In this study, down-conversion fluorescent powder of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+), which were the common three primary colors materials with long afterglow, were synthesized by high temperature solid state method. The blends of rare earth(RE) luminescent materials have been of interest to reinvest the luminescent characteristics of polyethylene terephtahalate(PET) luminous fiber. The scanning electron microscopy(SEM) and an inversion fluorescence microscope were used to characterize the surface morphology and the dispersion of inclusion. Through analysis of microcosmic morphology, three typical dispersions of luminescent particles were summarized. The X-ray diffraction indicated that the phase structure of fiber samples and crystal structure of luminescence materials kept complete after prilling and spinning. From the fluorescence spectra and CIE 1931 coordinates, it could be found that different combinations of luminous fibers were desired to obtain divers colors emission luminous fiber. And the fiber samples were a light sensation which could induct different excitation wavelengths and convert it down to different colors. The afterglow decay curve and its differential curve were summarized indicating the three decay stages. The decay curve and decay rate curve showed that the contents of Sr_2ZnSi_2O_7:Eu~(2+),Dy~(3+), SrAl_2O_4:Eu~(2+),Dy~(3+) and Y_2O_2S:Eu~(3+),Mg~(2+),Ti~(4+) had obvious influence on the afterglow of fiber samples.     

H2BPMPBD和TOPO协同萃取Ln3+的研究

研究了1,4-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)丁二酮(H2BPMPBD,简为H2A)和三正辛基氧化膦(TOPO)的氯仿溶液从硝酸介质中对Ln3+的协同萃取.用斜率法确定了萃合物的组成为LaA·HA·TOPO,考察了萃取剂浓度和溶液酸度对萃取机理的影响,测定了半萃取pH1/2值和萃取反应平衡常数Ks.e,求得了反应的焓变和熵变.     

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.     

Origin of the red luminescence in Sr_3Al_2O_6:Eu phosphor ——From the synergetic effects of Eu~(2+) and Eu~(3+)

In order to uncover the real origin of red luminescence from Sr_3Al_2O_6:Eu and the physical mechanisms that were involved in the dynamical process of luminescence, variant amount of Eu and Dy activated Sr_3Al_2O_6 phosphors were synthesized with the solid-state reaction and the combustion-assisted solid-state reaction, respectively, using the fine graphite powder or the mixed H_~(2+)N_2gases as a reducing agent. The phase was examined with XRD analysis and the photoluminescence properties were characterized by a fluorescence spectrometer. Although the phosphors possessed the same Sr_3Al_2O_6 phase, different emission colors(red or green) were obtained, relying on synthesis conditions. The simultaneous existence of Eu~(2+) and Eu~(3+) was not only observed in the emission and excitation spectra, but also identified with the near edge X-ray absorption fine structure spectroscopy(NEXAFS).The mixed valence(higher than +2 and less than +3) of Eu may be related with the six different sites of Sr, whose effective valence ranged from +1.5058 to +2.2698, in the crystal lattice of Sr_3Al_2O_6 that could accommodate Eu. Moreover, the reduction of Eu~(3+) to forming Eu~(2+) depended on the amount of Eu~(3+) or Dy~(3+) doped, due to the different energy barrier in each site of Sr that Eu had to overcome. The residual Eu~(3+), similar to the doped Dy~(3+), played an important role in supplying the hole for Eu~(~(2+)) to form a bound trap(Eu~(2+))* after excitation. During electron returning to the 4f~7 ground state of Eu~(2+), the red luminescence was radiated. Therefore, the synergetic effects of Eu~(2+) and Eu~(3+)(Dy~(3+)) produce red luminescence.     

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.     

Synergistic effect of crystal structure and concentration quenching on photoluminescence of Er~(3+) doped upconversion nanocrystals

YbF_(2.357), YbF_3, Ba_2 YbF_7, and Ba _2 upconversion nanocrystals doped with emitter Er~(3+) ion were synthesized in the same solvent system just with changing the molar ratio of Ba~(2+) to Yb~(3+) in the precursor, which corresponed to the crystal phases of rhombohedral, orthorhombic, tetragonal, and cubic, respectively. All the samples emitted both 660 nm red light and 543/523 nm green light which originated from Er~(3+)-4f~n electronic transitions ~4F_(9/2)-~4I_(15/2) and ~4S_(3/2)/~2H_(11/2)-~4I_(15/2), respectively. It was worth mentioning that YbF 3:Er~(3+), Ba_2 YbF_7:Er~(3+), and BaF_2:Er~(3+) could emit dazzlingly bright light even under the excitation of a 980 nm CW laser with output power of 0.1 W. Upconversion emission mechanism analysis indicated that the intensity ratio of red to green light highly depended on the synergistic effect of crystal structure, concentration quenching, and particle size, but were not sensitive to crystallinity as previously reported for NaL nF_4(Ln=lanthanide).     

Sub-10 nm lanthanide-doped SrFCl nanoprobes:Controlled synthesis,optical properties and bioimaging

Alkaline-earth dihalide nanocrystals(NCs) such as SrFCl, owing to their high chemical stability and low phonon energy, are excellent host materials for lanthanide(Ln~(3+)) doping to achieve desirable optical properties for various bioapplications, Herein, we report a novel strategy for the synthesis of sub-10 nm Ln~(3+)-doped SrFCl NCs with efficient upconverting and downshifting luminescence through a facile onestep hot-injection method. Utilizing the temperature-dependent upconverting luminescence(UCL) from the thermally coupled ~2H_(11/2) and ~4S_(3/2) levels of Er~(3+), we showed the potential of SrFCl:Yb,Er NCs as sensitive UCL nanoprobes for non-contact thermal sensing with a maximum detection sensitivity of 0.0066 K~(-1), which is among the highest values for thermal sensing based on Er~(3+)-activated UCL nanoprobes. Furthermore, by employing the intense downshifting luminescence from Tb~(3+) and Eu~(3+), we demonstrated the successful use of biotinylated SrFCl:Ce,Tb and SrFCl:Eu~(3+) nanoprobes for biotin receptor-targeted cancer cell imaging, thus revealing the great promise of SrFCl:Ln~(3+) nanoprobes for versatile bioapplications.     

Luminescent properties of Dy~(3+)/Eu~(3+) doped fluorescent glass for white LED based on oxyfluoride matrix

Rare earth ion-doped fluorescent glass has become a hotspot due to its characteristics.This work shows that the prepared Dy~(3+)and Dy~(3+)/Eu~(3+)doped glasses have white light emission under ultraviolet excitation.There is a higher yellow light/blue light(Y/B) value,indicating an increase in the covalentity of Dy-O,and decrease in the symmetry with the increasing concentration of dopants(Dy~(3+)).The correlated color temperature(CCT) can be effectively reduced by the red light emission of Eu~(3+),and the order of influence of excitation wavelength on CCT is 395 nm 382 nm 365 nm.The delay curve demonstrates the energy transfer from Dy~(3+)to Eu~(3+).The glass has the characteristics of anti-blue light damage and wide tunable color temperature,which illustrates that it has potential application in the field of white LED.     

VUV photoluminescence properties of KSrPO4:Dy3+ phosphor

White-light-emitting phosphors based on phosphate host matrix, KSrPO_4 doped with Dy~(3+), were prepared by solid state reaction and their VUV luminescent properties were firstly investigated. The excitation band peaking at 125-153 nm corresponding to the absorption of PO_4~(3-) group exhibits very strong absorption. The phosphors emit warm-white luminescence under vacuum ultraviolet excitation of 147 nm, which consists of three main emission peaks located at 475, 570 and 662 nm, respectively.According to the luminescence and color chromaticity of the optimal sample KSrPO_4:1 mol%Dy~(3+),1.3 mol%Li~+, it can be a potential candidate for mercury-free fluorescent lamps.     

Preparation and luminescence properties of rare-earth doped fiber with spectral blue-shift: SrAl_2O_4:Eu~(2+),Dy~(3+) phosphors/triarylsulfonium hexafluoroantimonate based on polypropylene substrate

The rare-earth doped fiber with spectral blue-shift based on long afterglow luminescent materials SrAl_2O_4:Eu~(2+),Dy~(3+) phosphors and an organic cationic photoinitiators-triarylsulfonium hexafluoroantimonate(TSHF) in the presence of polypropylene substrate(PP) was prepared by melt-spinning process. Scanning electron microscopy(SEM), infrared spectroscopy(IR), afterglow properties and luminescence properties were tested. The results of SEM and FTIR spectra showed that the fiber consisted of irregular particles and had independent structural constitution of SrAl_2O_4:Eu~(2+),Dy~(3+) phosphors, TSHF and polypropylene. Furthermore, it was observed that there existed the highest afterglow initial intensity for the fiber with the TSHF concentration of 5 wt.%. More interestingly, the emission peak shifted to blue area gradually as the TSHF doping increased. The rare-earth doped fiber was distributed on blue light area in the CIE 1931 chromaticity diagram, which showed more obvious blue-shift phenomenon than the yellow-green light of SrAl_2O_4:Eu~(2+),Dy~(3+) phosphors.     

正丙醇析相萃取BiI4-络阴离子的研究

试验了在氯化钠存在下,Bi3+以BiI4-络阴离子萃取到正丙醇相的最佳条件。结果表明,氯化钠能使正丙醇的水溶液分成两相,在分相过程中,Bi3+与碘化钾生成的BiI4-与质子化正丙醇(C3H7OH2+)形成的缔合物[BiI4-][C3H7OH2+]能被正丙醇相完全萃取。当正丙醇、碘化钾和氯化钠的浓度分别为30%(V/V)、6.0×10-3mol/L、0.2 g/mL时,Bi3+的萃取率达到99.2%以上,Fe2+、Co2+、Ni2+、Ag+、Mn2+、Cr3+、Ce3+、Zn2+和Al3+基本不被萃取,实现了Bi3+与上述金属离子的分离,对合成水样和锌铋合金中Bi3+的分离和测定,结果满意。     

红色长余辉发光材料BaMg_2Si_2O_7∶Pr,Mn的制备及性质研究

采用高温固相法合成了红色长余辉材料BaMg2Si2O7∶Pr,Mn,利用X晶体衍射仪、扫描电镜、荧光光谱、热释光测量仪等对材料的性能进行了表征,结果分析证明BaMg2Si2O7∶Pr,Mn以Mn2+为发光中心,Pr3+为共激活离子,在紫外光的照射下能够得到由Mn2+的4T1(4G)→6A1(6S)跃迁产生的峰值在666nm发射峰,产生红光发射,撤离激发光源后,能够产生余辉,且余辉时间可以持续达40分钟以上,基质中存在着Pr3+→Mn2+的能量传递,能够增强其荧光发射峰强度并对余辉性能有一定促进作用。     

Crystal-field analyses for trivalent lanthanide ions in LiYF_4

Based on the completely parametric crystal-field model, the energy level parameters, including free-ion parameters and crystal-field parameters, obtained by fitting the experimental energy level data sets of Ln~(3+) in LiYF_4 were systematically analyzed. The results revealed that the regular variation trends of the major parameters at relatively low site symmetry still existed. The g factors of ground states were calculated using the parameters obtained from least-squares fitting. The results for Ce~(3+), Nd~(3+), Sm~(3+), Dy~(3+) and Yb~(3+) were in good agreement with experiment, while those of Er~(3+) deviated from experiment dramatically. Further study showed that the g factors depended strongly on B_4~6, and a slightly different B_4~6 value of -580cm~(-1) led to g factors agreeing well with the experimental values.     

Co-Precipitation Synthesis and Spectral Characteristics of Long Afterglow Phosphor Y2O2 S： Sm^3＋, Mg^2＋ , Ti^4＋

Y2O2S：Sm^3＋, Mg^2＋, Ti^4＋ phosphor was synthesized by co-precipitation method. The crystalline structure of all synthesized phosphors was investigated by XRD. The result showed that all synthesized phosphors had a hexagonal crystal structure, which was the same as Y2O2S. The emission spectrum and excitation spectrum were measured, and the effect of Sm^3 ＋ molar ratio on the spectra was discussed. The emission spectra of the phosphors showed three emission peaks due to typical transitions of Sm^3 ＋ （4G5/2→6HJ ,J = 5/2, 7/2, 9/2）, and the emission peaks at 606 nm was stronger than others. With the increase of Sm^3 ＋ molar ratio, the emission intensity was strengthened. The excitation peaks were ascribed to the representative energy transition 4f→4f of Ti^4＋ phosphor prepared by co-precipitation method was Sm^3＋ ions. The results indicated that the Y2O2S ： Sm^3＋ , Mg^2＋ , an efficient long afterglow phosphor.     

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.     

Investigation of the temperature characteristic in SrB_4O_7:Sm~(2+) phosphor-in-glass by analyzing the lifetime of 684 nm

The SrB_4O_7:Sm~(2+) phosphor was synthesized by high temperature solid state reaction method. The phosphor-in-glass was prepared by mixing and firing the phosphor and TeO_2-ZnO glass precursor. The XRD results showed that the phosphor-in-glass was in amorphous phase because of the tiny mass fraction of phosphor in glass. The emission spectrum under the 355 nm excitation was measured, and it exhibited the same characteristic emission peaks as the phosphor sample. The temperature characteristic of the SrB_4O_7:Sm~(2+) phosphor-in-glass was discussed by analyzing the lifetime of 684 nm emission at various temperatures. The relative temperature sensitivity of 5%/K around 573 K was obtained for the temperature dependent lifetime, suggesting that the material in this study is a promising candidate for temperature sensor application.