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1.
A series of novel KBaSc2(PO4)3:Ce3+/Eu2+/Tb3+phosphors are prepared using a solid‐state reaction. X‐ray diffraction analysis and Rietveld structure refinement are used to check the phase purity and crystal structure of the prepared samples. Ce3+‐ and Eu2+‐doped phosphors both have broad excitation and emission bands, owing to the spin‐ and orbital‐allowed electron transition between the 4f and 5d energy levels. By co‐doping the KBaSc2(PO4)3:Eu2+ and KBaSc2(PO4)3:Ce3+ phosphors with Tb3+ ions, tunable colors from blue to green can be obtained. The critical distance between the Eu2+ and Tb3+ ions is calculated by a concentration quenching method and the energy‐transfer mechanism for Eu2+→Tb3+ is studied by utilizing the Inokuti–Hirayama model. In addition, the quantum efficiencies of the prepared samples are measured. The results indicate that KBaSc2(PO4)3:Eu2+,Tb3+ and KBaSc2(PO4)3:Ce3+,Tb3+ phosphors might have potential applications in UV‐excited white‐light‐emitting diodes.  相似文献   

2.
For the first time, a new langbeinite‐type phosphate, namely potassium terbium tantalum tris(phosphate), K2Tb1.5Ta0.5(PO4)3, has been prepared successfully using a high‐temperature flux method and has been structurally characterized by single‐crystal X‐ray diffraction. The results show that its structure can be described as a three‐dimensional open framework of [Tb1.5Ta0.5(PO4)3] interconnected by K+ ions. The TbIII and TaV cations in the structure are disordered and occupy the same crystallographic sites. The IR spectrum, the UV–Vis spectrum, the morphology and the Eu3+‐activated photoluminescence spectroscopic properties were studied. A series of Eu3+‐doped phosphors, i.e. K2Tb1.5–xTa0.5(PO4)3:xEu3+ (x = 0.01, 0.03, 0.05, 0.07, 0.10), were prepared via a solid‐state reaction and the photoluminescence properties were studied. The results show that under near‐UV excitation, the luminescence colour can be tuned from green through yellow to red by simply adjusting the Eu3+ concentration from 0 to 0.1, because of the efficient Tb3+→Eu3+ energy‐transfer mechanism.  相似文献   

3.
Three new isostructural 3D lanthanide metal–organic frameworks (Ln‐MOFs), {H[LnL(H2O)]?2 H2O}n ( 1‐Ln ) (Ln=Eu3+, Gd3+ and Tb3+), based on infinite lanthanide‐carboxylate chains were constructed by employing an ether‐separated 5,5′‐oxydiisophthalic acid (H4L) ligand under solvothermal reaction. 1‐Eu and 1‐Tb exhibit strong red and green emission, respectively, through the antenna effect, as demonstrated through a combination of calculation and experimental results. Moreover, a series of dichromatic doped 1‐EuxTby MOFs were fabricated by introducing different concentrations of Eu3+ and Tb3+ ions, and they display an unusual variation of luminescent colors from green, yellow, orange to red. 1‐Eu with channels decorated by ether O atoms and the open metal sites displays good performance for CO2 capture and conversion between CO2 and epoxides into cyclic carbonates.  相似文献   

4.
Four new three‐dimensional isostructural lanthanide–cadmium metal–organic frameworks (Ln–Cd MOFs), [LnCd2(imdc)2(Ac)(H2O)2]?H2O (Ln=Pr ( 1 ), Eu ( 2 ), Gd ( 3 ), and Tb ( 4 ); H3imdc=4,5‐imidazoledicarboxylic acid; Ac=acetate), have been synthesized under hydrothermal conditions and characterized by IR, elemental analyses, inductively coupled plasma (ICP) analysis, and X‐ray diffraction. Single‐crystal X‐ray diffraction shows that two LnIII ions are surrounded by four CdII ions to form a heteronuclear building block. The blocks are further linked to form 3D Ln–Cd MOFs by the bridging imdc3? ligand. Furthermore, the left‐ and right‐handed helices array alternatively in the lattice. Eu–Cd and Tb–Cd MOFs can emit characteristic red light with the EuIII ion and green light with the TbIII ion, respectively, while both Gd–Cd and Pr–Cd MOFs generate blue emission when they are excited. Different concentrations of Eu3+ and Tb3+ ions were co‐doped into Gd–Cd/Pr–Cd MOFs, and tunable luminescence from yellow to white was achieved. White‐light emission was obtained successfully by adjusting the excitation wavelength or the co‐doping ratio of the co‐doped Gd–Cd and Pr–Cd MOFs. These results show that the relative emission intensity of white light for Gd–Cd:Eu3+,Tb3+ MOFs is stronger than that of Pr–Cd:Eu3+,Tb3+ MOFs, which implies that the Gd complex is a better matrix than the Pr complex to obtain white‐light emission materials.  相似文献   

5.
A lanthanide‐complex‐based ratiometric luminescence probe specific for peroxynitrite (ONOO?), 4′‐(2,4‐dimethoxyphenyl)‐2,2′:6′,2′′‐terpyridine‐6,6′′‐diyl]bis(methylenenitrilo)tetrakis(acetate)‐Eu3+/Tb3+ ([Eu3+/Tb3+(DTTA)]), has been designed and synthesized. Both [Eu3+(DTTA)] and [Tb3+(DTTA)] are highly water soluble with large stability constants at ≈1020, and strongly luminescent with luminescence quantum yields of 10.0 and 9.9 %, respectively, and long luminescence lifetimes of 1.38 and 0.26 ms, respectively. It was found that the luminescence of [Tb3+(DTTA)] could be quenched by ONOO? rapidly and specifically in aqueous buffers, while that of [Eu3+(DTTA)] did not respond to the addition of ONOO?. Thus, by simply mixing [Eu3+(DTTA)] and [Tb3+(DTTA)] in an aqueous buffer, a ratiometric luminescence probe specific for time‐gated luminescence detection of ONOO? was obtained. The performance of [Tb3+(DTTA)] and [Eu3+/Tb3+(DTTA)] as the probes for luminescence imaging detection of ONOO? in living cells was investigated. The results demonstrated the efficacy and advantages of the new ratiometric luminescence probe for highly sensitive luminescence bioimaging application.  相似文献   

6.
《化学:亚洲杂志》2017,12(7):768-774
Bridged polysilsesquioxanes (BPs) show great potential in the development of lanthanide‐based luminescent materials, owing to their capacity to loading lanthanide complexes with high concentration and their flexible processability. A novel BP precursor, consisting of a C 3‐symmetrical benzene central core moiety, capable of sensitizing the luminescence of Eu3+ and Tb3+ is reported. Tunable, full‐color luminescent gels were facilely prepared by mixing the as‐synthesized precursor and Ln3+ ions in appropriate solvents. By either changing the Eu3+/Tb3+ molar ratio or altering the excitation wavelength, the emission colors of the final gels can be finely tuned. Additionally, the yellow‐colored emissive gel with a molar ratio of Eu3+ to Tb3+ of 0.5 can be used as an effective ratiometric luminescent sensor for distinguishing amines with lower pK a (<5) from those with higher pK a (>9).  相似文献   

7.
A series of Eu2+‐, Ce3+‐, and Tb3+‐doped Ca2Ga2SiO7 phosphors is synthesized by using a high‐temperature solid‐state reaction. The powder X‐ray diffraction and structure refinement data indicate that our prepared phosphors are single phased and the phosphor crystalizes in a tetrahedral system with the ${P\bar 42m}$ (113) space group. The Eu2+‐ and Ce3+‐doped phosphors both have broad excitation bands, which match well with the UV light‐emitting diodes chips. Under irradiation of λ=350 nm, Ca2Ga2SiO7:Eu2+ and Ca2Ga2SiO7:Ce3+, Li+ have green and blue emissions, respectively. Luminescence of Ca2Ga2SiO7:Tb3+, Li+ phosphor varies with the different Tb3+ contents. The thermal stability and energy‐migration mechanism of Ca2Ga2SiO7:Eu2+ are also studied. The investigation results indicate that the prepared Ca2Ga2SiO7:Eu2+ and Ca2Ga2SiO7:Ce3+, Li+ samples show potential as green and blue phosphors, respectively, for UV‐excited white‐light‐emitting diodes.  相似文献   

8.
Production of hybrid organic/inorganic complexes such as lanthanide phosphors in the nanodomain for human fingerprint visualization and anti‐counterfeiting ink under biocompatible UVA and blue light has not yet been studied that thoroughly. This paper presents the preparation of novel, bifunctional, green and red nanophosphors based on Eu3+ and Tb3+ complexes with quinolinone ligand (H2L). They have been prepared and characterized for latent fingerprint detection and anti‐counterfeiting ink applications. The analytical data confirm that the ligand acts in a monoanionic bidentate manner through OO donor sites, forming mononuclear complexes, formulated as [Ln(HL)3(C2H5OH)3] (Ln = Eu3+ or Tb3+; L = 1‐ethyl‐4‐hydroxy‐3‐(nitroacetyl)quinolin‐2‐(1H)‐one). The Eu3+ and Tb3+ complexes have nanospherical morphologies with average particle sizes of 17 and 5 nm, respectively. Pure red and green photoluminescence with long lifetime values has been obtained from the Eu3+ and Tb3+ complexes, respectively, under non‐harmful UVA and blue illumination. Latent fingerprint details, including their characteristic three levels, have been clearly identified from various forensic (non‐porous, semi‐porous, highly fluorescent porous) substrates using red (Eu3+) and green (Tb3+) nanophosphors. The green nanophosphor powder has a greater capability for visualizing latent fingerprints from highly fluorescent porous surfaces as compared to the red one. Both nanophosphor complexes have been used to develop luminescent ink for anti‐counterfeiting applications.  相似文献   

9.
Sr8MgCe(PO4)7:Eu2+,Mn2+ phosphor with whitlockite‐type structure was prepared by a combustion‐assisted solid‐state reaction. The crystal structure and luminescence properties were investigated. Under UV radiation, Sr8MgCe(PO4)7 host exhibits a violet‐blue emission band from Ce3+ ions. When Eu2+/Mn2+ are doped into the host, the samples excited with 270 nm UV radiation present multicolor emissions due to the energy transfer (ET) from Ce3+ to Eu2+/Mn2+. The emitting color of Sr8MgCe(PO4)7:Eu2+ can be tuned from violet‐blue to yellow‐green, whereas Sr8MgCe(PO4)7:Mn2+ can emit red light. Under excitation with long wavelength at 360 nm, Sr8MgCe(PO4)7:Eu2+ phosphor shows a broadband emission from 390 to 700 nm, which is attributed to the 4f65d1→4f7 transition of Eu2+ without the contribution from Ce3+ emission. Tunable full‐color emitting light can be achieved in the Eu2+ and Mn2+‐codoped Sr8MgCe(PO4)7 phosphor by ETEu–Mn through control of the levels of doped Eu2+ and Mn2+ ions. These results suggest that Sr8MgCe(PO4)7:Eu2+,Mn2+ phosphor has potential applications in NUV chip pumped white LEDs.  相似文献   

10.
A new stibium phosphate, lithium barium bis(antimony oxide) tris(phosphate), LiBa(SbO)2(PO4)3, was prepared by the molten salt method with LiF as the flux. The crystal structure consists of an original three‐dimensional anionic framework of [(SbO)2(PO4)3] built from PO4 tetrahedra sharing their corners with SbO6 octahedra. This framework delimits one‐dimensional tunnels where the lithium(I) and barium(II) ions are located. The UV–Vis spectrum shows that LiBa(SbO)2(PO4)3 was transparent from 350 to 800 nm, and is thus suitable as a luminescent host matrix. We then used Tb3+ and Eu3+ activators to test its luminous performance and the purities of the prepared phosphors were studied by powder X‐ray diffraction analysis with Rietveld refinements. Photoluminescence (PL) studies reveal that the emission spectra of 1 mol% RE3+‐doped (RE = Tb and Eu) samples can be excited by 371 and 394 nm light, emitting green and orange–red light, respectively, for Tb3+ and Eu3+. The CIE coordinates were measured to be (0.295, 0.571) and (0.6027, 0.3967), and the luminescent lifetimes were calculated as 0.178 and 1.159 ms, respectively.  相似文献   

11.
The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare‐earth ions doping and intrinsic emission of lead‐free double perovskite Cs2AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first‐principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5D47F6‐3) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+. By controlling Tb3+ ions concentration, the emission colors of Bi‐doped Cs2Ag(In1?xTbx)Cl6 NCs could be continuously tuned from green to orange, through the efficient energy‐transfer channel from self‐trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead‐free perovskite NCs and to expand their luminescence applications.  相似文献   

12.
Tb3+–Yb3+ co-doped Ca5(PO4)3F inverse opal photonic crystals were prepared by a self-assembly technique in combination with a sol–gel method. Upconversion luminescence characteristics of the inverse opals were investigated. The results indicate that photonic band gap has a significant effect on upconversion luminescence of Tb3+–Yb3+ co-doped Ca5(PO4)3F inverse opal. Significant inhibition of the green or blue upconversion luminescence was inspected if the photonic band gap overlapped with the emission band of Tb3+ ions.  相似文献   

13.
We have successfully synthesized Eu3+-doped TbPO4 nanowires, which are orderly organized to form bundle-like structure. A thermal treatment up to 600 °C does not modify the size, shape and structure of as-synthesized sample. Due to the energy overlap between Tb3+ and Eu3+, an efficient energy transfer occurs from Tb3+ to Eu3+. The effects of Eu3+ concentration and thermal treatment on the luminescent properties of Eu3+ are investigated. The increase of Eu3+ concentration leads to the increase of the energy transfer efficiency from Tb3+ to Eu3+, but also enhances the probability of the interaction between neighboring Eu3+, which results in the concentration quenching. With the heat-treatment, the luminescence of Eu3+ presents an obvious increase, but almost no change for the luminescence of Tb3+. This difference is explained based on the TGA, DTA, and fluorescent decay dynamics analyses.  相似文献   

14.
Cooperative performance of mixed‐valent Eu2+/Eu3+ in single‐compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu2+ oxidation. Using the tunable nature of the metal‐ion nodes in metal–organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu2+/Eu3+ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic‐ and sensitized‐emissions of Eu2+ and Eu3+, and long‐lived luminescence from charge transfer. Color rendering can be easily achieved by fine‐tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu2+/Eu3+ emissions provides outstanding properties for applications as self‐calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb3+ into the MOFs results in white light, utilizing all Eu2+,Tb3+, and Eu3+ emissions in a single crystalline lattice.  相似文献   

15.
A series of 12 dinuclear complexes [Ln2Cl6(μ‐4,4′‐bipy)(py)6], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – 12 , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4′‐bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl3 and 4,4‐bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln‐N‐MOFs ${\hbox{}{{\hfill 2\atop \hfill \infty }}}$ [Ln2Cl6(4,4′‐bipy)3] ? 2(4,4′‐bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, ( 1 , 4 – 8 ) were determined, showing an antenna effect through a ligand–metal energy transfer. The highest efficiency of luminescence is observed for the terbium‐based compound 7 displaying a high quantum yield (QY of 86 %). Excitation with UV light reveals typical emission colors of lanthanide‐dependent intra 4f–4f‐transition emissions in the visible range (TbIII: green, EuIII: red, SmIII: salmon red, DyIII: yellow). For the GdIII‐ and YIII‐containing compounds 6 and 1 , blue emission based on triplet phosphorescence is observed. Furthermore, ligand‐to‐metal charge‐transfer (LMCT) states, based on the interaction of Cl? with EuIII, were observed for the EuIII compound 5 including energy‐transfer processes to the EuIII ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln‐independent quantum yields in the related MOFs.  相似文献   

16.
采用液相法成功制备了MWCNTs负载NaGdF4:Tb3+,Eu3+纳米粒子的磁光热多功能复合纳米材料,并用XRD,SEM和EDS对其结构、组成和形貌进行了表征,结果表明:NaGdF4:Tb3+,Eu3+纳米粒子为六方晶相,形貌为球形且尺寸分布均匀,直径大约为25 nm,并且均匀的包覆在MWCNTs的表面;通过PL,VSM和HTC对复合纳米材料的发光性能,磁性能和光热转换性能进行了表征,采用MTT法对多功能复合纳米材料的生物相容性进行了评估,结果表明:MWCNTs-NaGdF4:Tb3+,Eu3+复合纳米材料具有良好的多色发光性能、磁性能、光热转换性能、低的毒性和良好的生物相容性。该种磁光热多功能复合纳米材料在生物标记、生物成像、肿瘤诊疗等领域有着广泛的应用前景。  相似文献   

17.
Herein, EuIII‐doped 3D mesoscopically ordered arrays of mesoporous and nanocrystalline titania are prepared and studied. The rare‐earth‐doped titania thin films—synthesized via evaporation‐induced self‐assembly (EISA)—are characterized by using environmental ellipsoporosimetry, electronic microscopy (i.e. high‐resolution scanning electron microscopy, HR‐SEM, and transmission electron microscopy, HR‐TEM), X‐ray diffraction, and luminescence spectroscopy. Structural characterizations show that high europium‐ion loadings can be incorporated into the titanium‐dioxide walls without destroying the mesoporous arrangement. The luminescence properties of EuIII are investigated by using steady‐state and time‐resolved spectroscopy via excitation of the EuIII ions through the titania host. Using EuIII luminescence as a probe, the europium‐ion sites can be addressed with at least two different environments within the mesoporous framework, namely, a nanocrystalline environment and a glasslike one. Emission fluctuations (5D07F2) are observed upon continuous UV excitation in the host matrix. These fluctuations are attributed to charge trapping and appear to be strongly dependent on the amount of europium and the level of crystallinity.  相似文献   

18.
We describe herein the synthesis and photophysical characterization of new lanthanide complexes that consist of a (9,9‐dimethylfluoren‐2‐yl)‐2‐oxoethyl or a (9,9′‐spirobifluoren‐2‐yl)‐2‐oxoethyl unit as the antenna, covalently linked to a 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid (DO3A) unit as the Ln3+ (Gd3+, Eu3+, Sm3+, Tb3+, Dy3+) coordination site. We were able to translate the spectroscopic properties of the innovative bipartite ligands into the formation of highly luminescent europium complexes that exhibit efficient emission (?se>0.1) upon sensitization in the near‐visible region, that is, with an excitation wavelength above 350 nm. The luminescence of the Eu3+complexes is clearly detectable at concentrations as low as 10 pM . Furthermore, the structural organization of these bipartite ligands makes the complexes highly soluble in aqueous solutions and chemically stable over time.  相似文献   

19.
A series of organic-inorganic hybrid material with chemically bonding have been prepared through the precursor (PDCA-Si) derived from 2-pyrrolidinone-5-carboxylic acid, which exhibits a self-organization cooperation interaction under the coordination to RE3+ (Eu3+, Tb3+). The pure organic silica hybrids (PDCA-Si) without RE3+ presents the small particle size and main blue luminescence with maximum peak 462 nm occupying a broad band from 425 to 550 nm. When Eu3+ and Tb3+ are introduced, the particle size of the hybrids increases, indicating the coordination effect has influence on the microstructure of hybrids. Besides, the corresponding Eu and Tb hybrids (Eu-PDCA-Si, Tb-PDCA-Si) show the characteristic red and green luminescence of Eu3+ and Tb3+, respectively, which suggests that the efficient intramolecular energy transfer process take place between carboxylic groups and lanthanide ions take place. The luminescence lifetimes and quantum efficiencies of them are determined and energy transfer efficiency between PDCA-Si and Eu3+ (Tb3+) is calculated.  相似文献   

20.
采用优化的高温固相方法制备了稀土离子Eu3+和Tb3+掺杂的La7O6(BO3)(PO42系荧光材料,并对其物相行为、晶体结构、光致发光性能和热稳定性进行了详细研究。结果表明,La7O6(BO3)(PO42:Eu3+材料在紫外光激发下能够发射出红光,发射光谱中最强发射峰位于616 nm处,为5D07F2特征能级跃迁,Eu3+的最优掺杂浓度为0.08,对应的CIE坐标为(0.610 2,0.382 3);La7O6(BO3)(PO42:Tb3+材料在紫外光激发下能够发射出绿光,发射光谱中最强发射峰位于544 nm处,对应Tb3+5D47F5能级跃迁,Tb3+离子的最优掺杂浓度为0.15,对应的CIE坐标为(0.317 7,0.535 2)。此外,对2种材料的变温光谱分析发现Eu3+和Tb3+掺杂的La7O6(BO3)(PO42荧光材料均具有良好的热稳定性。  相似文献   

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