Enhancement of structure stability and luminescence intensity of LiYF_4:Ln~(3+) nanocrystals

LiYF_4 nanocrystals with tetragonal structure were adopted as the host materials for the phosphors and scintillators owing to the low phonon energy and high optical transparency. LiYF_4:Ln~(3+)(Ce~(3+),Eu~(3+)) nanocrystals were fabricated by solvothermal method. Under UV excitation, they could emit visible light. In order to improve the luminescence intensity, the method of co-doping LiYF_4 nanocrystals with Sc was adopted. Sc~(3+) ions could reduce the lattice expansion caused by the doping of Ce~(3+) or Eu~(3+) whose ionic radius was larger than Y~(3+). Crystal structure of Li(Y,Sc)F_4:Ln~(3+) kept much more stable and the luminescence intensity could be significantly enhanced when the concentration of Sc was a moderate value. Thermoluminescence was employed to analyze the electron traps in Li(Y,Sc)F_4:Ce~(3+). Results suggested that the suppression of the generation of electron traps with the co-doping of Sc contributed to the enhancement of luminescence intensity of LiYF_4:Ce~(3+).     

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 Cr~(3+)-sensitized upconversion luminescence of LiScSi_2O_6:Cr~(3+)/Er~(3+)

Broadband sensitization is an effective strategy to enhance the upconversion luminescence(UCL) of lanthanide ions.Herein,novel UC materials LiScSi_2 O_6:Cr~(3+)/Er~(3+)(LSS:Cr~(3+)/Er~(3+)) were synthesized by high-temperature solid state reaction and their luminescent properties were investigated.LSS:Cr~(3+)/Er~(3+)has the broadband absorption in the spectral range of 600-800 nm,and meanwhile shows green UC emissions of Er~(3+)upon pumping Cr~(3+) by the 690 nm laser.The UCL of LSS:Cr~(3+)/Er~(3+)belongs to the twophoton process and is attributed to the energy transfer upconversion mechanism.The effects of the Cr~(3+)and Er~(3+)concentration as well as the Yb~(3+)introduction were also studied.LSS:Cr~(3+)/Yb~(3+)/Er~(3+) exhibits the interesting dual-mode UCL,capable of generating the UCL of Cr~(3+) upon pumping Yb~(3+)ions and the UCL of upon pumping Cr~(3+) ions.This research might promote the development of novel broadband Cr~(3+)-sensitized UC materials.     

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.     

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.     

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.     

Synthesis and characterization of NaYF_4:Yb~(3+),Er~(3+)@silica-N=folic acid nanocomplex for bioimaginable detecting MCF-7 breast cancer cells

Upconversion nanophosphors are new promising nanomaterials to be used as biolabels for detection and imaging of cancer cells.These nanophosphors absorb long-wavelength excitation radiation in the infrared or near infrared region and emit shorter wavelength,higher energy radiation from ultraviolet to infrared.In this paper,we studied the hydrothermal method and optical properties of the functionalized NaYF_4:Yb~(3+),Er~(3+)for biomedical application.After synthesis,these NaYF_4:Yb~(3+),Er~(3+)nanophosphors were functionalized with aminosilanes and folic acid.Folic acid binds to the folate receptor on the surface of MCF-7 breast cancer cells and this binding promotes internalization of the nanophosphors via endocytosis.The sizes of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA(folic acid) nanophosphors can be controlled with length of the rod about 300-800 nm and diameter of the rod about 100-200 nm.Phase structure of NaYF_4:Yb~(3+),Er~(3+)is in hexagonal crystal system.The photo luminescence(PL) spectra of the functionalized NaYF_4:Yb~(3+),Er~(3+)@silica-N=FA nanophosphors were measured.These nanophosphors emit in red color with the strongest band at 650 nm under 980 nm excitation.This result can provide NaYF_4:Er~(3+),Yb~(3+)@silica-N=FA complex for developing fluorescence label and image tool in cancer biology and medicine.     

稀土离子与钙调素相互作用的研究进展

稀土离子由于配位环境与钙离子具有相似性,能够取代钙离子与钙调素发生作用,对钙调素的结构、构象及生物功能产生影响。各种光谱及生物化学实验研究表明,不同稀土离子与钙调素作用时,在作用力的强弱程度、结合位点、结合序及结合位点的相互作用具有各自的特殊性,本文概述了稀土离子La3+、Ce3+、Pr3+、Nd3+、Sm3+、Eu3+、Gd3+、Tb3+、Ho3+、Er3+和Lu3+等与钙调素的相互作用及对钙调素生物功能产生的影响。     

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.     

Effect of RE~(3+) electronegativities on luminescence property of Ba_5Si_8O_(21):Eu~(2+) persistent phosphor

A series of Ba_5Si_8O_(21):0.02Eu~(2+),0.09RE~(3+) persistent phosphors were synthesized by the solid-state reaction method.The measurement results of photoluminescence(PL),phosphorescence and thermoluminescence(TL)were analysed and discussed.The XRD results showed that samples codoped with different RE~(3+) were Ba_5Si_8O_(21) single pure phase.Under the excitation,all samples exhibited a broad Eu~(2+) characteristic emission,and the La~(3+) co-doped sample emitted the brightest photoluminescence even though its persistent luminescence property was the worst because of the weakest electronegativity.However,Nd~(3+) electronegativity was suitable,thus after activation,the Ba_5Si_8O_(21):Eu~(2+),Nd~(3+) sample had the best persistent luminescence performance with the highest phosphorescence intensity and the persistent luminescence decay time beyond 8 h.The Nd~(3+) co-doped sample also had the largest thermoluminescence integral area which proved effectively it had longer persistent luminescence time.The luminescence mechanism was also proposed to study the photoluminescence and persistent luminescence process.These results showed that RE~(3+) electronegativities were distinctly important for persistent phosphors and choosing suitable electronegativity codopant was conducive to enhancing the phosphorescent performance.     

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).     

Na_2WO_4:Eu~(3+),Tb~(3+)光致发光材料的发光性质和能量传递

利用溶胶-凝胶法,将激活离子Eu~(3+)和Tb~(3+)以单一或混合的形式掺入体系得到了光致发光材料.分别研究了材料中激活离子Eu~(3+)和Tb~(3+)的含量及其离子之间的能量传递关系.主要利用材料的三维荧光光谱,激发光谱和发射光谱对其的发光性质进行了分析;结果发现,材料中有两个发光中心,分别为Eu~(3+)和Tb~(3+),在不同的波长光的激发下得到的材料的红绿色发光强度不同,而且Eu~(3+)和Tb~(3+)的掺杂浓度比对发光色度影响很大.所以可以根据选择最适合的Eu~(3+)和Tb~(3+)的浓度比来控制材料的发光色,也可以通过不同的激发波长对材料的色度进行微调.     

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.     

Highly sensitive up-conversion phosphor for optical thermometry:CaLaAl_3O_7:Er~(3+)/Yb~(3+)

Herein, we reported Er~(3+)/Yb~(3+) co-doped CaLaAl_3O_7 up-conversion phosphors synthesized via solid state reaction, which was further explored as a new optical thermometry. The luminescent properties of Er~(3+) or Er~(3+)/Yb~(3+) doped CaLaAl_3O_7 phosphor was studied in detail. The two-photon process for the green emissions of Er~(3+) were confirmed by the power-dependent luminescence. The up-conversion optical temperature sensing performances of the Er~(3+)/Yb~(3+)-codoped CaLaAl_3O_7 phosphor were investigated based on the FIR technique. The maximum sensitivity of this phosphor can reach about 0.00345 K~(-1) at 453 K, which reveals this phosphor can be a promising candidate for optical thermometry devices.     

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.     

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.     

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.     

Preparation and upconversion luminescence modification of YbPO_4:Er~(3+) inverse opal heterostructure

Photonic crystal heterostructures composed of YbPO_4:Er~(3+) inverse opal and polystyrene opal were prepared via a template-assisted process, which exhibited two photonic band gaps. The microstructure,phase and optical properties of photonic crystal heterostructures were investigated by x-ray diffraction,scanning electron microscopy, fluorescence spectroscopy, absorption spectroscopy, fluorescence lifetime,etc. The upconversion emission suppression caused by single photonic band gap from the following YbPO_4:Er~(3+) inverse opal or the upper opal was observed. The upconversion luminescence was strongly suppressed due to the two photonic band gap overlapping effect caused by the following YbPO_4:Er~(3+) inverse opal or the upper opal. The modified mechanisms of upconversion luminescence were discussed by the upconversion luminescence lifetime of YbPO_4:Er~(3+) photonic crystal heterostructures. The results demonstrated the modified upconversion luminescence is attributed to the photon trapping caused by Bragg reflection of photonic crystal heterostructures.     

Surface-effect on detection ability of fluorescent Eu(btc) metal-organic frameworks to metal ions

Eu(btc)metal organic frameworks(MOFs)were prepared by co-precipitation method via 1,2,4-benzenetricarboxylic acids(H3btc)connecting with Eu³⁺ions,and the morphology was controlled from compact spherical to irregular honeycomb by adjusting the pH of reaction solutions.The luminescence properties of Eu(btc)MOFs are found to be related to the surface morphology of products,and the compact spherical one performs stronger emission intensity.The sensing ability of Eu(btc)MOFs to 11 kinds of metal ions was investigated and a prominent quenching effect occurrs in Fe³⁺,or Ni²⁺solutions.Based on UV—vis absorption analysis,an“ion-fence”model presents the competition to absorb exciting light between Eu(btc)MOFs and adsorbed metal ions.Based on Stern-Volmer equation,the Eu(btc)detection is found with higher Ksv value and a lower detection limit.Meanwhile,a higher sensing efficiency is confirmed in the Eu(btc)MOFs with loose honeycomb due to aggravating porous surface offering much more sites for metal ions.